The world number 10 will line up with former England internationals Teddy Sheringham and Phil Neville and ex-Denmark goalkeeper Peter Schmeichel at the iconic West Course on the outskirts of London on May 21.
"I am really looking forward to a round of golf with a few of my Man United heroes...I believe they have some silky golfing skills too," twice major winner McIlroy said in a news release on Tuesday.
Former defender Neville, who is now on the coaching staff at Old Trafford, is hoping he does not freeze on the big day.
"Peter, Teddy and I have all competed on the world stage and we love our golf but that won't stop us feeling the nerves when we step on to that first tee," he said.
"It's going to be a great day and who better to have on our team, offering a few words of advice, than Rory McIlroy. I can't wait."
To celebrate 60 years of the European Tour's flagship event, a host of sporting celebrities will take part in the pre-tournament pro-am including former cricketers Ian Botham, Brian Lara, Andrew Strauss and Allan Lamb.
Tim Henman and Greg Rusedski will represent the world of tennis while Gianfranco Zola, Andriy Shevchenko and Glenn Hoddle are among the former footballers who will take part.
Former Olympic rowers Steve Redgrave and Matthew Pinsent will swap oars for golf clubs and ex-Formula One world champion Damon Hill is another sportsman expected to compete.
(Reporting by Tony Jimenez, Editing by Ed Osmond)
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