US Open winner Bryson DeChambeau and world number two Jon Rahm of Spain will play together in the first two rounds of the Masters in the pairings unveiled Tuesday.
Joining them Thursday and Friday at Augusta National will be South Africa's Louis Oosthuizen, the 2010 British Open champion.
The field of 93 will start off the first and 10th tees in threesomes on Friday and Saturday before a cut to the low 50 and ties for the weekend.
DeChambeau is the long-driving favorite after his overwhelming first major victory at Winged Foot in September while Rahm chases his first major crown 40 years after idol Seve Ballesteros win his first Masters.
They go off the 10th tee at 07:33 on Thursday and the first tee at 11:38 Friday.
Defending champion Tiger Woods, hoping to match Jack Nicklaus with a record sixth Masters win, will play alongside reigning British Open champion Shane Lowry and US Amateur winner Andy Ogletree.
They start two groups and 22 minutes behind DeChambeau and Rahm on the same tees and days.
Starts come off both tees to help ensure a finish before darkness in an event traditionally staged in April but postponed to November due to the Covid-19 pandemic.
Other notable pairings include world number one Dustin Johnson going off alongside fellow American Patrick Cantlay and four-time major champion Rory McIlroy, who is chasing a green jacket to complete a career Grand Slam.
They start at noon Thursday off the first tee and 07:55 Friday off the 10th tee.
Two-time Masters winner Bubba Watson joins compatriot Matthew Wolff and England's Tommy Fleetwood off the 10th tee at 11:27 Thursday and the first tee at 07:22 Friday.