DeChambeau's group will start from the first tee at 13:29 CET and be followed around the challenging par-70 layout by a threesome comprised of past US Open champions Matt Fitzpatrick, Wyndham Clark and Gary Woodland.
Since joining LIV Golf in June 2022, DeChambeau has recorded seven top-10 finishes in 12 majors, including last year's US Open triumph at Pinehurst. He now looks to become the event's first repeat winner since Brooks Koepka in 2018.
Red-hot world number one Scheffler, who counts the PGA Championship among his three wins in his last four starts, will also start from the first tee at 19:25 CET in the company of Collin Morikawa and Viktor Hovland.
Rory McIlroy, who completed the career Grand Slam at the Masters but finished well out of contention at the PGA Championship, will head out from the 10th tee at 13:40 CET in the company of Shane Lowry and Justin Rose.
Phil Mickelson, US Open runner-up a record six times and needing a win this week to complete the career Grand Slam, will start from the 10th tee alongside Cameron Smith and Brian Harman at 14:02 CET.
Dustin Johnson, who won the US Open when it was last held at Oakmont in 2016, was placed in a high-profile group with Jordan Spieth and Jon Rahm and will head out from the 10th tee at 19:14 CET.
Amateur Matt Vogt, a 34-year-old dentist and former Oakmont caddie who qualified to play in the year's third major last week, will hit the tournament's opening shot from the first tee at 12:45 CET