On a second set point, Zvonareva fired an inside-out forehand, wrong-footing Williams with such severity that she lost her footing and fell on her butt behind the baseline.
Eliminating grass stains from her pink Nike dress figures to be far less challenging than removing the rust from her game for Williams, who looked fit but was breathing heavily at times during her 3-6, 7-6 (5), 7-5 loss to the top seed.
Defending her Wimbledon title with the miniscule match play of just one tuneup tournament in the past 50 weeks, Williams' path to a third consecutive Wimbledon crown looks as easy to navigate as the prospect of moon-walking across the River Thames with her Wilson racket bag strapped to her back.
"It would be monumental in my mind if Serena pulled off a win," says ESPN analyst and Hall of Famer Chris Evert. "You can never, ever count her out. But I don't know how it's humanly possible for someone to take a year off like that and have gone through what she's been through physically. It would almost shock me if she [won], but knowing Serena and the way she's come back before, you can never count her out."
Indeed, if Williams can work through the first week, she becomes more dangerous with each passing round. She has reached the Wimbledon final in six of her past eight All England Club appearances and is the most explosive player in the game when fully fit.
The plot lines for the women's field are thicker than the Centre Court grass.
Will five-time champion Venus Williams or four-time champ Serena continue the decade of dominance that has seen the sisters combine to win nine of the past 11 Wimbledon championships?
Can reigning Roland Garros champion Li Na, who lost to Serena in the 2010 quarterfinals, contest her third consecutive major final?
Will Maria Sharapova, who reached the Roland Garros semis on her worst surface, summon the form she showed as a precocious power in 2004, when the then-17-year-old Russian shoved Serena aside in a shocking straight-sets upset to master her first major?
Here's a preview of eight women to watch at Wimbledon.
No. 1 Caroline Wozniacki
Strengths: Desire and a determined defensive game built on consistent strokes and quick court coverage can make squeezing the ball past Wozniacki as challenging as slipping into the royal box. Wozniacki has played high-percentage tennis in collecting a WTA-best five tournament titles this year and has reached the semifinals or better in nine of 13 tournaments.
Weaknesses: Finishing points and fatigue. Wozniacki has played 53 matches this season, and that schedule seemed to take a toll in Paris, where she looked listless in a 6-1, 6-3 third-round loss to Daniela Hantuchova -- her earliest major exit in two years. Her serve is attackable, and her topspin forehand can land short in the court against the tour's heaviest hitters.
Question marks: Can she create enough offense to combat the firepower from flat-ball hitters who have pushed her around the court at times?
Outlook: Although the 2006 Wimbledon junior champ has yet to surpass the fourth round in four prior appearances, she's capable of a quarterfinal result this year if the draw breaks to her benefit.
No. 3 Vera Zvonareva
Strengths: The 2010 singles and doubles finalist knows her way around grass, is balanced off both backhand and forehand, and can close at net. Her 3-hour, 12-minute win over Serena at Eastbourne was her first win over Williams in five years and one that should empower her for Wimbledon.
Weaknesses: Emotional implosions have held her back in the past, and while Zvonareva can take the ball early, she does not hit quite as heavy as some of the premier power players.
Question marks: How will the sometimes-volatile Vera, who has worked to tame her tendency to blow up amid match stress, withstand the pressure of defending her final ranking points?
Outlook: A return to the final might well elude her, but the feisty fighter should reach the second week.
No. 4 Li Na
Strengths: The French Open champ has been at her best in the biggest matches, boasting a 7-2 record versus top-10 opponents and reaching the finals at both the Australian Open and Roland Garros. Li is one of the game's best pure athletes, a clean ball-striker, and carries the confidence of a freshly crowned major champion.
Weaknesses: The 29-year-old from China can be streaky sometimes and has a tendency to get down on herself when missing the mark with her flat shots.
Question marks: How will Li respond to the added attention in her bid to become the first woman since Serena in 2002 to sweep Roland Garros and Wimbledon in succession?
Outlook: If she can compete with the conviction she showed in Melbourne and Paris, a third straight major final appearance is within her reach.
No. 5 Victoria Azarenka
Strengths: An aggressive baseliner whose bold strokes can pose problems for even top players, Azarenka's ability to dictate play was evident in Miami when she swept Kim Clijsters, Zvonareva and Sharapova in succession to take the title.
Weaknesses: Mastering the game between the ears has been as tough as controlling play between the lines. Azarenka has retired from nine matches in the past 18 months.
Question marks: Self-imposed pressure has been a stumbling block. The 21-year-old Belarusian has failed to surpass the third round in four of five Wimbledon appearances.
Outlook: One of these days, Azarenka will break through to her first major semifinal, and while that might be beyond her reach this time, she is a quarterfinal candidate.
No. 6 Maria Sharapova
Strengths: One of only three former champions in the field, the 6-foot-2 Sharapova can control play on the strength of her screaming shots and is one of tennis's most mentally tough players. She is a winner, a warrior and a superior shot-maker who relishes the Grand Slam stage.
Weaknesses: Mobility is not an asset, her second serve offers little margin for error, her low volley can be sketchy and she seldom hits smashes, making her net play suspect.
Question marks: Pained by shoulder and elbow injuries in recent years, Sharapova is five years removed from her last final-four appearance and has been vulnerable to early-round upsets, suffering second-round setbacks twice in the past three years.
Outlook: If she can serve with authority and play the type of first-strike tennis she showed in Paris, Sharapova is a serious threat to return to the final for the first time in seven years.
No. 8 Petra Kvitova
Strengths: The only left-hander in the top 20 can impose her game on almost any woman when she's playing well. The 21-year-old Czech owns a crackling serve, crunching groundstrokes and fine feel in the front court, and is adept at playing creative combinations.
Weaknesses: Inexperience. Kvitova had never won a Wimbledon match before surging to the semis last year as a 62nd-ranked dark horse sporting braces.
Question marks: She arrives at SW19 carrying a career-high ranking and the burden of high expectations; how will she respond?
Outlook: Kvitova has the game to win Wimbledon one day, and although she might need a bit more maturity to do it, a semifinal return is possible.
No. 26 Serena Williams
Strengths: An immortal champion armed with an imposing serve John McEnroe calls "the greatest serve in the history of women's tennis" set a Wimbledon record with 89 aces in claiming the Rosewater Dish for the fourth time last July. The most convincing closer of this generation owns an eye-popping 13-3 record in major finals.
Weaknesses: Questions surround Serena's fitness and lack of match play. Since winning Wimbledon without surrendering a set, she's played only two matches in the past 50 weeks due to a right-foot injury and pulmonary embolism.
Question marks: Can she shake off the rust and find her game fast enough to become the first woman since Steffi Graf in 1993 to collect three consecutive Wimbledon titles?
Outlook: If the seventh seed can serve with power and precision and fight through the first week, she is capable of winning her 14th major championship.
No. 33 Venus Williams
Strengths: The five-time champion's searing serve, forceful flat groundstrokes and athleticism are all assets on grass.
Weaknesses: Venus' second serve can be shaky, and she is prone to periods of slapping her forehand into net when she loses the timing and correct contact point on that shot.
Question marks: Can she find the winning gear in her game in a year in which she's played only two tournaments?
Outlook: Venus celebrates her 31st birthday Friday, and if she's connecting on her serve, she is a threat to reach her ninth Wimbledon semifinal.