The 40-year-old defied some of the toughest conditions the tournament has witnessed in recent years to card a seven-under-par 65, signing for nine birdies and coming home in 31.
The brilliant effort was 10 shots better than the average score on a day when only 11 players in the 94-strong field finished in red figures.
Hoffman is just the third player in Masters history to lead by five shots after 18 holes. Craig Wood was the first in 1941 and went on to complere a wire-to-wire win.
Jackie Burke Jnr also burst out of the blocks in 1955 but he lost out to Cary Middlecoff.
Only time will tell if Hoffman can emulate Wood, but this isn’t the first time that the Californian’s name has been up near the top of the leaderboard in this event.
Two years ago, he was second after the first and second rounds then fourth after 54 holes before finishing joint-ninth behind Jordan Spieth.
“It was a dream,” said Hoffman of this eye-catching start. “You hit the shots that you’re sort of looking at, and then the hardest part is to convert the putts.
“I was able to do that and I got some good numbers coming down the stretch.”
A four-time PGA Tour winner, the leader had just 25 putts in a round that saw him hit 14 greens in regulation.
“I got a little bit lucky,” he added. “I was fortunate I put myself in spots to be able to make putts.
“I was able to make some longer putts, which you’re just trying to die it up there close to the hole.”
The challenge for Hoffman now is to try and back up his flying start. He’s hoping to draw on that experience of being in contention in 2015.
“Yeah, I’m going to feed off that the rest of the week,” he admitted. “Today you just sort go with it. There wasn’t, I wouldn’t say, a ton of pressure today.
“Obviously going to sleep on the lead at a major championship here at Augusta National is not going to be the easiest thing.
“But I look forward to it, and I look forward to the challenge the next three days.”
His nearest challenger is fellow American William McGirt, who was on the first tee in the morning to join in a tribute to four-time winner Arnold Palmer before getting his own Masters career off to a great start.
“This is a lifelong dream,” said the 37-year-old, who made his PGA Tour breakthrough by winning the Memorial Tournament last year. “You don’t know if this moment will ever happen.
“Believe it or not, I was not nervous at all today. I really even surprised myself. When I heard, “Fore, please, William McGirt now driving,” I almost shed a tear.
“But I realised I had to get up there and I had 40 seconds to hit it, so I better get it done quick.”
Both McGirt, who said he has both Scottish and Irish ancestry, and his wife, Sarah, had joined ‘Arnie’s Army’ earlier in the day as Augusta National paid its tribute to Palmer, who passed away at the age of 87 last September.
“We were never going to miss the Opening Ceremony this morning, or the ceremonial tee shot,” said McGirt.