Hernandez, the first Venezuela pitcher to start for the All-Stars, is 11-2 with a 2.12 ERA. He is the second Seattle pitcher to start an All-Star Game following Randy Johnson in 1995 and 1997.
"Just throw zeros out there and get my team to win, that's all I got to do," Hernandez said.
NL manager Mike Matheny of the Cardinals chose the ace of his own staff. Wainwright is 12-4 with a 1.83 ERA and three complete games in 19 starts. It will be the 11th All-Star start by a Cardinals pitcher.
"Aside from having the ability to win two World Series with the St. Louis Cardinals, I think this has to be one of the highlights of my baseball career to this point," Wainwright said. "One of the coolest things I can say I did is to start a big league All-Star Game."
Los Angeles Dodgers ace Clayton Kershaw also could have gotten the nod to start for the NL following a first half that saw him go 11-2 with a 1.78 ERA, a stretch that included a no-hitter and a 41-inning scoreless streak. But he said Wainwright is deserving.
"You're not going to not pick your guy," Kershaw told reporters, referring to Cardinals manager Matheny.
"Adam deserves it. I have all the respect in the world for Adam."
Yankees shortstop Derek Jeter, a 14-time All-Star who is playing his final season, will lead off for the AL.
"It's a rare and unique opportunity," AL manager John Farrell of the Boston Red Sox said. "At the same time we are able to celebrate a player who is not only a champion, but a guy that sets the bar that I think all players should aspire to. The way he has handled himself with class, with performance -- no doubt a Hall of Famer."
Wainwright said he is looking forward to pitching to Jeter.
"I have been in the big leagues for nine years. I've never faced him," Wainwright said. "I'm very excited about it, just to say I faced the best. And he is undoubtedly one of the best to ever play his position, one of the greatest Yankees of all time."
The Los Angeles Angels' Mike Trout bats second and plays left, followed by Seattle second baseman Robinson Cano, Detroit first baseman Miguel Cabrera, Toronto right fielder Jose Bautista, Baltimore designated hitter Nelson Cruz, Orioles center fielder Adam Jones, Oakland third baseman Josh Donaldson and Kansas City catcher Salvador Perez.
Pittsburgh center fielder Andrew McCutchen leads off for the NL, followed by Los Angeles Dodgers right fielder Yasiel Puig, Colorado shortstop Troy Tulowitzki and Arizona first baseman Paul Goldschmidt. Miami's Giancarlo Stanton will be the DH and bat fifth. He will be followed by Milwaukee third baseman Aramis Ramirez, Philadelphia second baseman Chase Utley, Milwaukee catcher Jonathan Lucroy and Brewers left fielder Carlos Gomez.
Information from the Associated Press was used in this report.