Australian Scott claimed the 2013 title by beating Argentina's Angel Cabrera in a play-off, and starts the defence of his crown at Augusta on Thursday.
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The 33-year-old is set to tee of with American Dufner, who will be gunning for his second major title after winning the PGA Championship in 2013.
But the experience will be a new one for 19-year-old Fitzpatrick, making his first appearance at The Masters following a tied 44th finish at last year's British Open.
Two more of last year's major winners will start their respective quests for the green jacket together, with Phil Mickelson, winner of the British Open in 2013 and a three-time champion at Augusta, grouped with reigning US Open champion Justin Rose and four-time major winner Ernie Els.
Bubba Watson, winner in 2012, features in a talented group that also contains former world number one Luke Donald and Spain's world number six Sergio Garcia.
Sweden's Henrik Stenson enjoyed an impressive 2013 season, becoming the first player to win both the PGA Tour's FedEx Cup and the European Tour's Race to Dubai, but the world number three has yet to win a major and starts his Masters campaign alongside world number four Jason Day and home hope Dustin Johnson.