Lee and Crowe set off together in the sixth group of the morning with veteran former champion Larry Mize after golf legends Jack Nicklaus, Tom Watson and Gary Player hit the ceremonial tee shots under grey skies on Thursday.
Canadian Mike Weir had the honour of hitting the first shot, 20 years after his Masters victory.
Weir is playing with Kevin Na, one of the 18 LIV Golf players in the 88-player field at the year's first major.
The LIV contingent features former Masters champions Phil Mickelson, Dustin Johnson, Sergio Garcia, Bubba Watson, Patrick Reed and Charl Schwartzel.
Tournament favourite and world No.1 Scottie Scheffler, bidding to become the fourth player to go back-to-back at Augusta, was due to go out in the third-last group at 1.36pm (3.36am AEST) with Max Homa and amateur Sam Bennett.
"I feel pretty good. Game's in a good spot," Scheffler said on Wednesday.
"I liked the way I was swinging it the first couple of days here, just the practice rounds ... and I'm ready for the tournament to start."
Other high-profile groups include reigning PGA Championship winner Justin Thomas, world No.3 Jon Rahm and Cameron Young.
Rory McIlroy, seeking a win to complete the career grand slam of golf's four majors, was due out in the day's penultimate group with WGC Match Play champion Sam Burns and exciting young Korean Tom Kim.
Tiger Woods, making only his second start this season given his limited schedule after a February 2021 car crash, is playing with Xander Schauffele and Viktor Hovland.
Woods, who defied the odds at the 2019 Masters when he returned from spinal fusion surgery to win a fifth green jacket, is now trying to push the envelope again.
The 15-times major winner said this week he does not know how many more Masters tournaments he has left and while his game and endurance are better than a year ago his body aches more.
Australia's 2013 champion Adam Scott is in the group behind Woods with Americans Patrick Cantlay and Kurt Kitayama.
Cameron Smith, bidding to win successive majors after his stunning British Open triumph at St Andrews last July, had been grouped behind his compatriot Scott alongside former Presidents Cup teammates Sungjae Im and 2021 Masters champion Hideki Matsuyama.
Jason Day is the only Australian with an afternoon tee time, off with 2007 champion Zach Johnson and American amateur Gordon Sargent.
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