Luke Donald will take on Bubba Watson in the first of 12 singles matches that will ultimately decide the Ryder Cup.
USA captain Davis Love III opted to put big-hitting Watson out first, followed by close friend and Ryder Cup partner Webb Simpson, who will go head-to-head with Ian Poulter.
Keegan Bradley and Rory McIlroy make up a fascinating third pairing as both captains chose to load the top of their teams with quality in a bid to establish early momentum.
Francesco Molinari has been given the task of anchoring the European side by captain Jose Maria Olazabal, and that means he'll face a rematch with Tiger Woods, who beat him comfortably at Celtic Manor two years ago.
Woods' position is perhaps testament to the fact that he's played the back-nine better than any of his compatriots despite struggling this week, whereas Olazabal has clearly attempted to keep his weaker putters at the back of his pack.
Full draw:
Bubba Watson v Luke Donald (1703 BST)
Webb Simpson v Ian Poulter (1714)
Keegan Bradley v Rory McIlroy (1725)
Phil Mickelson v Justin Rose (1736)
Brandt Snedeker v Paul Lawrie (1747)
Dustin Johnson v Nicolas Colsaerts (1758)
Zach Johnson v Graeme McDowell (1809)
Jim Furyk v Sergio Garcia (1820)
Jason Dufner v Peter Hanson (1831)
Matt Kuchar v Lee Westwood (1842)
Steve Stricker v Martin Kaymer (1853)
Tiger Woods v Francesco Molinari (1904)
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