No. 1-ranked Rory McIlroy will be joined by countryman Graeme McDowell of Northern Ireland in the first foursomes (alternate shot) match that begins at 8:20 a.m. ET against Americans Jim Furyk and Brandt Snedeker.
Three of the four rookies on U.S. captain Davis Love III's team are getting started immediately, led by Snedeker, who captured the Tour Championship on Sunday along with the PGA Tour's FedEx Cup. Keegan Bradley and Jason Dufner also will play for the first time in the Ryder Cup.
That means Masters champion Watson and U.S. Open champion Simpson will be cheering on their teammates -- at least as the matches get started Friday.
"These guys are not really rookies," Love said. "Brandt Snedeker has been playing as well as anybody since The Open Championship, and he's hot. Got him with a guy that's got a lot of experience.
"Obviously, the first tee Friday morning of the Ryder Cup is going to be a pretty exciting, loud place, and we wanted some guys that we felt like could handle that situation and that wanted to get out of the gate and get going. Those are two guys we felt like were perfect for the first time."
In the second match at 8:35 a.m., Spain's Sergio Garcia and England's Luke Donald take on Americans Phil Mickelson and Ryder Cup rookie Keegan Bradley. Garcia and Donald are 4-0 together and present one of Europe's strongest teams. They are a combined 22-8-5.
"I'm really looking forward to it," said Donald, who lives in Chicago. "We've obviously both got unbeaten records in foursomes and we have played well together in the past. We've got a great record together and it should be a great match against two very good players in Phil and Keegan.
"They obviously know each other well but Sergio and I do and we have had some great success together. We are very comfortable with each other and we are both playing very well, so we are looking forward to it and hoping to keep our unbeaten records going."
In the third match at 8:50 a.m., England's Lee Westwood will partner with Italy's Francesco Molinari against Americans Zach Johnson and the rookie Dufner. Westwood never has played with Molinari, but has a 16-11-6 record and is making his eighth appearance in the Ryder Cup. Molinari is the only European playing in the morning with a losing Ryder Cup record.
The final match at 9:05 a.m. features Tiger Woods and Steve Stricker against Englishmen Ian Poulter and Justin Rose, who were 2-1 together four years ago at Valhalla. Poulter is 8-3 in the Ryder Cup, but two of his losses have come against Woods. Stricker and Woods were 2-1 two years ago in Wales and 4-0 at the 2009 Presidents Cup, but they lost their last two matches together -- at the 2010 Ryder Cup and 2011 Presidents Cup.
"We are excited to go back at it again and try to win a point," Stricker said. "It's going to be fun. A lot of excitement and anticipation leading up to the start of the matches, and to get out there in the morning, we are really looking forward to it.
"It's going to be tough playing Poulter and Justin Rose; they are both playing well. Every match is tough but it's fun to get out there and get going right away in the morning."
Said Poulter: "It was always looking like Justin and I would be playing together and that we would be out in the first session and it is going to be a really great match, I just know it is. I hinted to Justin, just before going on stage, that it was my gut feeling that we would get Tiger and Strick and that is what we have got.
"Tiger and Strick are a very good pairing and they are going to come out at us with all guns blazing and will have all the local support, obviously, and we know we will have to play well to beat them."
Love is sitting Watson, Simpson, Dustin Johnson and Matt Kuchar. European captain Jose Maria Olazabal decided to keep his only rookie, Belgium's Nicolas Colsaerts, on the sideline, along with Paul Lawrie, Martin Kaymer and Peter Hanson.
The Ryder Cup pits a 12-man team of Europeans against a 12-man American squad. There are four foursomes matches in the morning followed by four four-ball matches (best ball) in the afternoon, with the first afternoon match scheduled for 1:05 p.m.
The captains will submit their afternoon pairings late Friday morning.
Love hinted strongly that he has a plan he will stick to and it seems to include getting those who will watch in the morning on the course in the afternoon. And he's got two very likely pairings in Johnson-Kuchar and Watson-Simpson. The later duo played well together last November at the Presidents Cup in Melbourne, where they went 3-1.
Olazabal made it clear he wanted to get off to fast start, hence putting McIlroy and McDowell in the first group.
"We are not hiding anything," Olazabal said. "We are not second-guessing here. We are just going out and try to win points, period, that's it. That's the only way I see we might have a chance of winning this event. We have to go for it. I know we are playing away. The crowds are going to be on their side. They set up the course to their liking.
"So, you know, at the end of the day, you have to make a bunch of birdies out there to win points. So just send the best players out there and see if they can perform well, and manage to win those points."
Joked McDowell: "We are going to use the world No. 1's power and precision and I will just knock a few tap-ins in."
There are eight points available Friday, and the same format is played on Saturday. There are 12 singles matches Sunday for a total of 28 points. The format is match play, and no match will go beyond the 18th hole, meaning matches can be halved.
To win the Ryder Cup, 14½ points are necessary, and if the event ends in a 14-14 tie, Europe retains the Cup based on its 2010 victory at Celtic Manor.