The Australian, who last year became the first player from his country to win the Masters, carded a three-under 69, which could have been even better had he not found water en route to a double-bogey five at the treacherous 12th yesterday.
It was the best first round by a defending Masters champion since Jose Maria Olazabal shot a 66 in 1995.
Scott tucked himself in just one stroke back from Bill Haas, a 31-year-old American ranked 31st in the world who sank a five-footer at the last for the day's best round of 68.
Tied for fourth, a further stroke back, was a sextet comprising Americans Kevin Stadler, Gary Woodland, Jimmy Walker and Brandt Snedeker as well as Jonas Blixt of Sweden and K.J. Choi of South Korea.
Tournament favorite Rory McIlroy was among a large group of players bunched on 71.
Scott opened confidently with a birdie and was four under after 10 holes before he hit into the water at the 12th for the first time in his career.
"I feel like I am playing really well," Scott said. "I felt I played good enough to shoot in the 60s today so it was good to make that par save at the last.
"Very happy the way I played tee to green. I hit the one poor shot at 12 which cost me a couple of shots.
"Very pleased to get off to such a good start and there is no doubt that winning the Masters last year has made me more comfortable on the first tee than I've ever been in the past because I didn't have the legs jangling for six or seven holes like usual, so that was enjoyable for me today."
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