Former British Open winner Smith, reigning US Open champion DeChambeau and 10 others will contest LIV Golf's Miami event from Friday before parachuting into Augusta National from next Thursday.
The three-day event at Trump National Doral is just LIV Golf's fifth this year.
DeChambeau has played only one 72-hole tournament since missing the cut at The Open last July, while Smith filled his boots in a four-event Australian swing late last year.
LIV members Sergio Garcia, Dustin Johnson, Phil Mickelson, Jon Rahm, Patrick Reed, Charl Schwartzel and Bubba Watson have all won the Masters while Brooks Koepka is a five-time major winner and two-time Masters runner-up.
Former world No.2 Smith hasn't won an individual event since 2023.
Question marks around his form - and decision to leave the PGA Tour after his 2022 Open triumph - have grown after a middling start to his 2025 LIV campaign.
DeChambeau held a share of the Masters halfway lead before fading to finish tied-sixth with Smith last year.
"For me personally, I like having time off, getting ready for these events, focusing on them, and getting my game into a good place, getting a strategy and game plan set up," the American said of his quieter schedule.
"If anything, I think it's been a tremendous help for me personally, giving myself a little bit more time to get ready for these events, and it's honestly been a blessing for me.
"I was so grateful to be there and having fun and competing and being at the top of that leaderboard (at the Masters last year).
"So yeah, was I feeling pressure? Yeah.
"Was I doing it for all of LIV? Sure, you can say that. For me, I'm just out there trying to win a golf tournament, and if that does great for LIV, then that's awesome."
Koepka's feeling good about his game after near misses at Augusta in 2019 and 2023.
"Every time you go play Augusta, I feel like your knowledge gets a little bit better," he said.
"I've got a good understanding of the golf course, how to play it for certain pins, different wind directions, things like that.
"Everything seems to be piecing together nicely. I like where I'm at," he said.
"Just focused a lot on ball striking ... and touch around the greens, because you're going to need that at Augusta."
10°C