Padraig Harrington of the European team lines up a shot during his practice round prior to the 2008 Ryder Cup at Valhalla Golf Club on September 18, 2008 in Louisville, Kentucky. (Andrew Redington/Getty Images)
Ireland's Harrington partners Swede Robert Karlsson for holders Europe, while Mickelson pairs with rookie Anthony Kim to lead off for the U.S. team in the first of four alternate shot matches to start the action at Valhalla Golf Club.
Europe's formidable duo of world number five Sergio Garcia of Spain and 12th-ranked Briton Lee Westwood anchor the foursomes session, taking on home-crowd favourite Kenny Perry and Jim Furyk in the fourth contest.
Fifteen minutes after the opening match starts at 0805 (1205 GMT), Britain's Paul Casey and Henrik Stenson of Sweden square off against Texans Justin Leonard and Hunter Mahan.
The third match pits Ian Poulter and fellow-Briton Justin Rose against Americans Stewart Cink and Chad Campbell.
Europe are aiming for a fourth successive victory, having enjoyed lopsided wins over the U.S. in the last two meetings.
