The world number one McIlroy will join forces with Spaniard Garcia - the man who ran him so close at The Open in July - to take on Phil Mickleson and Keegan Bradley in the last match of the opening morning.
McIlroy was victorious with Graeme McDowell in the first session of fourballs at Medinah two years ago but was always unlikely to reprise that link at Gleneagles.
McIlroy, McDowell and the pair's former management company have been involved in legal wrangles in recent months, with McDowell suggesting that they were only likely to join up in the foursomes.
Justin Rose and Henrik Stenson wil get the Europeans' defence of the trophy under way against Bubba Watson and Webb Simpson - with the latter duo an expected partnership after Simpson had hinted they would play together.
Rickie Fowler and rookie Jimmy Walker will face Thomas Bjorn and 2012 hero Martin Kaymer in match two, while Ian Poulter is the only non-debutant in match three.
With two newcomers in Jordan Spieth and Patrick Reed joining forces for the United States, Ryder Cup specialist Poulter will likely be tasked with offering his experience to home favourite Stephen Gallacher.
Friday's fourballs in full:
1 - Bubba Watson and Webb Simpson versus Justin Rose and Henrik Stenson
2 - Rickie Fowler and Jimmy Walker versus Thomas Bjorn and Martin Kaymer
3 - Jordan Spieth and Patrick Reed versus Stephen Gallacher and Ian Poulter
4 - Phil Mickleson and Keegan Bradley versus Sergio Garcia and Rory McIlroy