Rory McIlroy and Graeme McDowell will launch Europe’s bid to retain The Ryder Cup against Jim Furyk and Brandt Snedeker in Friday’s opening foursomes match.
The Northern Irish pair, who teamed up three times in Europe’s victory at The Celtic Manor Resort, were chosen by José María Olazábal to lead out at Medinah.
Unbeaten foursomes pair Luke Donald and Sergio Garcia will look to extend their incredible record against Phil Mickelson and Keegan Bradley in game two, before Lee Westwood and Francesco Molinari take on Jason Dufner and Zach Johnson.
The final game of the morning session also promises to be a classic as English pair Ian Poulter and Justin Rose face World Number Two Tiger Woods and Steve Stricker.Woods and Stricker boast a 6-2 winning record together, but their last two games were the 6 and 5 beating by Westwood and Donald in Wales two years ago and then a 7 and 6 loss to Adam Scott and K J Choi at the start of last November's Presidents Cup.
They did not play together again that week after that.
It means the four left out by Olazábal, who shed a few tears during the opening ceremony at the first mention of the late Seve Ballesteros, were Scot Paul Lawrie, Germany's former World Number One Martin Kaymer, Swede Peter Hanson and Belgian newcomer Nicolas Colsaerts.
The quartet kept waiting to play by Love were his two Major winners this year - Masters Tournament champion Bubba Watson and US Open Champion Webb Simpson - plus Dustin Johnson and Matt Kuchar.
It would have been a huge shock if McIlroy and McDowell were not together again.
Close friends and compatriots, they had one win, one half and one loss two years ago, but won three out of four in the 2009 Seve Trophy in Paris and have twice been Omega Mission Hills World Cup partners as well.
In Donald, Garcia and Westwood Europe can call on three players with outstanding foursomes records in the event.
Donald will be looking to make it a perfect seven out of seven.
His first four wins in 2004 and 2006 came with Garcia as his partner and two years ago he won with Poulter and then with Westwood.
Garcia is unbeaten in nine foursomes, eight of them victories, while Westwood has not lost any of his last ten games in the format going back to 1999.
His partners in that time have been Darren Clarke, Garcia, Colin Montgomerie, Kaymer and Donald - and now he links up with the Italian whose debut two years ago came alongside his brother Edoardo.
A month after that Molinari pipped Westwood to his first World Golf Championships title in Shanghai - with the best of the rest nine shots further back.
Garcia remains the only teenager ever to appear in the match, his debut in 1999 coming a month after he and Woods battled for the US PGA Championship at Medinah.
Jesper Parnevik was his first partner and they won their opening three games and got a half in the other, while in subsequent foursomes the Spaniard has won with Westwood, Donald and Olazábal.
Rose and Poulter won two of their three games together four years ago, Rose not making the 2010 match despite winning twice in America that summer.
Mickelson has won only two of his last 14 pairs games in the event, but was always expected to start with Bradley in his ninth appearance, an American record.
Olazábal told the crowd in his speech his side "have every intention of taking it (the cup) back home" with them and also managed to pay his latest tribute to his former partner Ballesteros, who died in May last year following a long battle with a brain tumour.
"Of course I can't forget a great friend in the name of Seve Ballesteros," he said. "He was a special man. I believe Seve reflected the core of Ryder Cup values - no quitting and be prepared to chase any adversity.
"From him I learnt what true passion is all about. Seve, we miss you."
All eight omitted from the opening session will be hoping to enter the fray in the afternoon fourballs.
It is the first time since 1995 - Mickelson's debut - that neither he nor Woods have been involved in the opening game.
Snedeker's quick pace played a part in Love's decision to go with him and Furyk first.
The hardest part of Love's day, though, was telling "four of the best golfers in the world" they would be sitting on the bench all morning.
He described Woods and Stricker - and also Johnson and Dufner - as "pretty cool customers at the end".
McIlroy said: "I can't wait. Leading the side off we are going to go out there and get the blue on the board early.
"It is a great honour to lead Europe out and to be honest they are not the opponents we were expecting.
"We know that their team is so strong all the way through, but it was a little surprise to see a rookie in their first group."
McDowell added: "We are going to use the World Number One's power and precision and I will just knock a few tap-ins in.
"I am very proud to be playing alongside my great friend and the greatest player on the planet.
"I was expecting Phil and Keegan to go first, but obviously Davis has his strategies.
"Tomorrow morning's session is hugely important and José María has stressed that. We really feel that it is very important to make a fast start.
"We are pretty pumped for this whole thing."
Donald said: "We've obviously both got unbeaten records in foursomes and we have played well together in the past.
"It should be a great match against two very good players. They obviously know each other well, but Sergio and I do and we have had some great success together.
"Obviously Phil has a lot of experience and Keegan is a rookie, but it's not a pairing that surprises you because they play a lot of golf together.
"But we've had some success against Phil before and hopefully we can again tomorrow.
"It should be a great atmosphere with Phil playing and hopefully I will get some support as I live in Chicago and Sergio obviously has some special memories from here." He was runner-up to Woods in the 1999 US PGA.
Garcia added: "He's my best friend on Tour and we get on great in foursomes together.
"We are going to try as hard as we can to bring back a point for the European Team."
Friday morning foursome matches:
7.20am Rory McIlroy & Graeme McDowell v Jim Furyk & Brandt Snedeker
7.35am Luke Donald & Sergio Garcia v Phil Mickelson & Keegan Bradley
7.50am Lee Westwood & Francesco Molinari v Jason Dufner & Zach Johnson
8.05am Ian Poulter & Justin Rose v Steve Stricker & Tiger Woods