Ryder Cup captains, Davis Love (L) of the US and Europe's Jose Maria Olazabal
Rory McIlroy and Graeme McDowell will begin Europe's defence when the 39th Ryder Cup begins at Medinah on Friday.
The Northern Irishmen will kick off the foursomes matches at 0720 (1320 BST) against Jim Furyk and Brandt Snedeker.
Luke Donald and Sergio Garcia resume their unbeaten partnership against Phil Mickelson and Keegan Bradley.
Lee Westwood and Francesco Molinari take on Jason Dufner and Zach Johnson, while Ian Poulter and Justin Rose face Tiger Woods and Steve Stricker.
The one slight surprise for Europe was that Italy's Molinari was paired with Westwood, but Europe captain, Jose Maria Olazabal defended his decision.
"It might surprise you, but when you look at Francesco's game, he's a steady player," said Olazabal, who played in seven Ryder Cups.
"He's straight off the tee, he hits good iron shots. When I look at foursomes, I want to have players who are consistent and are steady from tee to green."
The European side have won four of the last five Ryder Cups and six of the last eight against the USA, including two years ago in Wales, when the score was 14½-13½.
US captain, Davis Love said Snedeker's fine recent form had been a key factor in sending him out first, despite this being his maiden Ryder Cup.
"We wanted to get Brandt going - Brandt likes to get out there and get after it," said Love, who played in six Ryder Cups.
"Phil and Keegan are a little bit excited to be playing, too, so get them going. And then we've got some pretty cool customers at the end that can handle whatever happens in the last two matches."
Olazabal's team will be marginal underdogs over the long fairways and fast greens of Medinah Country Club, 20 miles west of Chicago.
Love has promised "fired-up" crowds over the three-day contest, with 40,000 expected to throng the course each day for what promises to be one of the closest ever Ryder Cups.
The USA's sole success this century came at Valhalla four years ago and Love will lean heavily on the experience of 14-time major winner Woods, Mickelson and Furyk as he attempts to steer a team containing four debutants to victory.
Olazabal hopes to inspire his side with the memory of his late friend and team-mate Seve Ballesteros, who helped reinvigorate a previously US-dominated contest with a succession of European wins in the 1980s and 1990s.
Ballesteros died last year but his image is emblazoned on his successors' bags, and his iconic outfit of navy trousers and jumper and white polo shirt will be worn by the team over the weekend.