The Northern Irishman will tee off at 11:05 with Team Europe four and a half points away from a famous victory in France after finishing 10-6 ahead on Saturday.
He will be followed by Paul Casey, who takes on Brooks Koepka, and Justin Rose who faces Webb Simpson.
Other notable match-ups include Jon Rahm against Tiger Woods, Ian Poulter taking on Dustin Johnson and Francesco Molinari against Phil Mickelson.
Alex Noren and Bryson DeChambeau are the final pairing of the day and they will tee off at 13:17.
Europe know that the magic 14 and a half total will mean they will win back the Ryder Cup after losing two years ago.
Thomas Bjorn's men head into the final day in a commanding position after winning five points over the course of Saturday.
Team USA have not overturned a four point deficit since 1999 at Brookline and the odds are heavily stacked against them to achieve the same success.
Tommy Fleetwood and Italian Molinari maintained their perfect record, beating Tiger Woods on two occasions earlier today and breaking records in the process.
Debutant Fleetwood became the first rookie in history to win all four of his matches so far.
Heading into Saturday with a 5-3 lead, Europe continued their momentum in the morning and surged ahead to make the score 8-4.
Henrik Stenson and Rose made it 9-4 with a 2&1 victory over Johnson and Koepka.
Bubba Watson and his partner Simpson along with Spieth and Thomas ensured the US remained in the hunt.
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