The draw means Woods will be on the course with his former caddie, Steve Williams, who now carries a bag for Scott.
Williams has drawn criticism for comments directed at Woods since he was fired by the golfer four months ago, causing a stir and leading to anticipation that Woods and Williams would face each other -- albeit indirectly -- this week.
The U.S. team of Woods and Steve Stricker drew Scott and K.J. Choi from the International team when the captains announced their lineups Wednesday.
International captain Greg Norman, after the pairings were announced, said having Woods and Scott in the anchor match would be great for the event.
U.S. captain Fred Couples said he and Norman didn't plan for it to happen that way, but that "it worked out awesome."
Despite winning 13 majors with Woods, Williams called Scott's victory at the WGC-Bridgestone Invitational in August the biggest of his career. He also drew ire for a racial remark directed at Woods during a caddie awards dinner two weeks ago.
The first five matches on Thursday are, with the International teams listed first:
Ernie Els and Ryo Ishikawa vs. Bubba Watson and Webb Simpson; Geoff Ogilvy and Charl Schwartzel vs. Bill Haas and Nick Watney; Aaron Baddeley and Jason Day vs. Dustin Johnson and Matt Kuchar; Retief Goosen and Robert Allenby vs. Phil Mickelson and Jim Furyk; and Kyung-Tae Kim and Y.E. Yang vs. Hunter Mahan and David Toms.