AUGUSTA, 6 Apr 2017, (AFP) - The American birdied four of his last five holes to post a seven under par 65 and move ahead of countryman William McGirt, with Lee Westwood mounting a remarkable late charge through the field to get to two under.
The Englishman has six top tens at Augusta National since 2010 - including last season's tie for second - and he made five birdies in a row from the 13th to put himself well in contention once again.
The day belonged to Hoffman, however, playing just his fourth Masters with the experience of sitting in second place after rounds one and two back in 2015.
There was a strong European Tour presence in the group at one under, with Englishmen Matthew Fitzpatrick, Justin Rose and Andy Sullivan, and Spaniard Sergio Garcia all six off the lead.
World Number Two Rory McIlroy was then in the group at level par alongside South Africa's Ernie Els, Dane Søren Kjeldsen, Irishman Shane Lowry and Belgian Thomas Pieters, a shot clear of defending champion Danny Willett.
Dustin Johnson, the World Number One, came into the week looking for a third consecutive European Tour title but was forced to withdraw with a back injury after a fall on Wednesday.
Hoffman was level par after seven holes but back-to-back birdies on the eighth and ninth kick-started his round before a back nine of 31. He holed a 15-footer on the 12th and then two lengthy efforts on the 14th and 15th before putting his tee-shot and approach on the 16th and 17th to three feet.
"The putts started going in the hole, as simple as that sounds," he said. "I hit it pretty solid in the wind, got away with a few shots and then I was able to make those 15-20 footers in the wind which was nice.
"I just kept hitting my spots and out here with the wind you end up having 20-footers and that's sort of what you're looking for. I was able to pour those in coming down the stretch which was nice and then I hit a few real close at the end which is always a good bonus.
"Obviously going to sleep on the lead at a Major Championship here at Augusta National is not going to be the easiest thing. I look forward to it and I look forward to the challenge the next three days."
McGirt was making his Masters debut and made birdies on the second, fifth, 13th and 16th to go with a bogey on the third.
Westwood was three over at the turn after bogeys on the fifth, seventh and ninth but came roaring back in stunning style. A 25-footer on the 13th started the run before two 12-foot putts had him back at level par. A beautiful tee-shot to five feet on the 16th made it four in a row before another smart approach on the next had the 23-time European Tour winner in third.
"I just made a couple of putts on the back nine and hit it a little bit closer," he said. "It was just a matter of being patient and not being too frustrated with being three over on the front nine.
"I didn't get aggressive on the tenth, I didn't get too aggressive at 11, just playing into the right spots, did the same at 12 just waiting for something to happen.
Three-time winner Phil Mickelson was at one under alongside fellow Americans Kevin Chappell, Jason Dufner and Russell Henley.
Pieters had been the first man to threaten to blow the field away as he got to five under after ten holes but made two double-bogeys on the way in, while McIlroy moved in the other direction, recovering from being three over after eight holes.
Willett also fought back well after being three over after two holes and would have finished level but for a bogey on the last.