World number one McIlroy, who lost in the final match last year to American Hunter Mahan, is the top seed in the Bobby Jones bracket and will play Ireland's Shane Lowry who secured his place in the tournament following Phil Mickelson's withdrawal.
Tiger Woods, a three-time WGC-Accenture Match Play winner, leads the Ben Hogan section and is up against fellow American Charles Howell III in Wednesday's first round.
Englishman Luke Donald, winner of the event in 2011, will take on Germany's Marcel Siem in the Sam Snead category while South Africa's Louis Oosthuizen is pitted against Scotland's Richie Ramsay in the Gary Player bracket.
The WGC-Accenture Match Play Championship first round draw is as follows:
Bobby Jones bracket
(1) Rory McIlroy v (64) Shane Lowry, (32) Rickie Fowler v (33) Carl Pettersson, (16) Dustin Johnson v (49) Alexander Noren, (17) Graeme McDowell v (48) Padraig Harrington, (8) Bubba Watson v (57) Chris Wood, (25) Jim Furyk v (40) Ryan Moore, (9) Charl Schwartzel v (56) Russell Henley, (24) Zach Johnson v (41) Glen Day
Gary Player bracket
(4) Louis Oosthuizen v (61) Richie Ramsay, (29) Branden Grace v (36) Robert Garrigus, (13) Keegan Bradley v (52) Marcus Fraser, (20) Ernie Els v (45) Fredrik Jacobson, (5) Justin Rose v (60) KJ Choi, (28) Bill Haas v (37) Nicolas Colsaerts, (12) Sergio Garcia v (53) Thongchai Jaidee, (21) Matt Kuchar v (44) Hiroyuki Fujita
Ben Hogan bracket
(2) Tiger Woods v (63) Charles Howell, (31) Gonzalo Fernandez-Castaño v (34) Francesco Molinari, (15) Webb Simpson v (50) David Lynn, (18) Peter Hanson v (47) Thomas Bjorn, (7) Lee Westwood v (58) Rafael Cabrera Bello, (26) Martin Kaymer v (39) George Coetzee, (10) Jason Dufner v (55) Richard Sterne, (23) Hunter Mahan v (42) Matteo Manassero
Sam Snead bracket
(3) Luke Donald v (62) Marcel Siem, (30) Paul Lawrie v (35) Scott Piercy, (14) Steve Stricker v (51) Henrik Stenson, (19) Nick Watney v (46) David Toms, (6) Adam Scott v (59) Tim Clark, (27) Jamie Donaldson v (38) Thorbjørn Olesen, (11) Ian Poulter v (54) Stephen Gallacher, (22) Bo Van Pelt v (43) John Senden