Scott made a clutch 15-foot putt at the second extra hole to stay alive then sank a seven-foot birdie at the next to become the fourth Australian to win at Colonial, joining Bruce Crampton, Bruce Devlin and Ian Baker-Finch.
"I certainly didn't play perfect this week, making a few errors, but it's the way you come back and get it done and I felt like I certainly played like one of the best players in the world out there on the back nine," Scott told reporters after becoming the first player to complete the so-called Texas Slam, following victories at the Houston Open (2007), Byron Nelson Championship (2008) and Texas Open (2010).
"It's a real honour for me to win here. I was determined because I really wanted to win them all here in Texas."
The week was not all smooth sailing for Scott, who was four-over after nine holes on Thursday and also double-bogeyed the ninth on Sunday to dig himself into another hole.
But he recovered with three quick birdies, including a 40-footer at the 14th that gave him the lead and prompted a punch of the air with an outstretched index finger, as if to offer a reminder that he is number one.
He and Dufner shot 66 to finish on nine-under-par 271, one shot ahead of American Nicholas Thompson and Swede Freddie Jacobson.
Dufner, the reigning PGA Championship winner, looked set to claim his fourth tour title when he stuffed a nine-iron into four feet at the second extra hole.
But the newly-married Scott, 33, calmly drained his birdie attempt to set the stage minutes later for his first victory of the year.
"A ball-striker like Jason is going to hit one in close sooner or later and he did on 17," Scott said. "To make the putt was huge."
The final round began with 36 players within four strokes of the lead, but in the end the cream came to the top as Scott, who needed to finish 13th or better to stay atop the world rankings, found an extra gear as all of his rivals except Dufner stalled.
"I’m trying not to put too much pressure on myself to have to win every week to stay number one," said Scott.
(Reporting By Andrew Both in Cary, North Carolina; Editing by Frank Pingue)
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