Jordan Spieth and Patrick Reed were drawn in the same group for the WGC-Dell Technologies Match Play, while Dustin Johnson was handed a better passage.
Spieth and Reed combined four times for the United States during last year's Presidents Cup, earning 3.5 points in their team's success over the International side.
However, they will be opponents at the Austin Country Club beginning Wednesday after being drawn in Group 4.
Charl Schwartzel and Li Haotong are also in the blockbuster group, with the winner to advance to the last 16.
World number one and defending champion Johnson is in Group 1 alongside Kevin Kisner, Adam Hadwin and Bernd Wiesberger.
Coming off his win at the Arnold Palmer Invitational, 2015 champion Rory McIlroy was drawn alongside Brian Harman, Jhonattan Vegas and Peter Uihlein in Group 6.
Two-time champion Jason Day is alongside Louis Oosthuizen, the man he beat in the 2016 final, Jason Dufner and James Hahn in Group 8.
Group 1 – Dustin Johnson, Kevin Kisner, Adam Hadwin and Bernd Wiesberger.
Group 2 – Justin Thomas, Francesco Molinari, Patton Kizzire and Luke List.
Group 3 – Jon Rahm, Kiradech Aphibarnrat, Chez Reavie and Keegan Bradley.
Group 4 – Jordan Spieth, Patrick Reed, Li Haotong and Charl Schwartzel.
Group 5 – Hideki Matsuyama, Patrick Cantlay, Cameron Smith and Yusaku Miyazato.
Group 6 – Rory McIlroy, Brian Harman, Jhonattan Vegas and Peter Uihlein.
Group 7 – Sergio Garcia, Xander Schauffele, Dylan Frittelli and Shubhankar Sharma.
Group 8 – Jason Day, Louis Oosthuizen, Jason Dufner and James Hahn.
Group 9 – Tommy Fleetwood, Daniel Berger, Kevin Chappell and Ian Poulter.
Group 10 – Paul Casey, Matthew Fitzpatrick, Kyle Stanley and Russell Henley.
Group 11 – Marc Leishman, Branden Grace, Bubba Watson and Julian Suri.
Group 12 – Tyrrell Hatton, Charley Hoffman, Brendan Steele and Alex Levy.
Group 13 – Alex Noren, Tony Finau, Thomas Pieters and Kevin Na.
Group 14 – Phil Mickelson, Rafa Cabrera Bello, Satoshi Kodaira and Charles Howell III.
Group 15 – Pat Perez, Gary Woodland, Webb Simpson and Kim Si-woo.
Group 16 – Matt Kuchar, Ross Fisher, Yuta Ikeda and Zach Johnson.