Hoffman slipped with five bogeys in six holes between sixth and 11th.
Hoffman shot an early birdie to move to eighth-under, even as Garcia, one group behind, birdied first three in a row.
Then Hoffman began unraveling from the sixth and Garcia kept rolling on igniting hopes of an emotional Sunday, which coincides with the legendary Seve Ballesteros' 60th birthday.
Garcia, who shot 71 on first day, was on fire in front nine with four birdies and one bogey to move to three-under for the day.
More From This Section
Overnight second, Willie McGirt, a first-timer at Augusta, dropped late bogeys on 14th and 18th for a round of 73 after going out first today.
He was the clubhouse leader at two-under 142 and overall third.
Lee Westwood, two-under in first round, had a eventful two-over front nine with four bogeys and two birdies.
Apart from Garcia others making a move were Ryan Moore, three-under through 16, 22-year-old Spaniard Jon Rahm, reckoned to be a dark horse, was two-under through eight holes. Moore was now one-under as was Rahm.
Top-50 and ties and those within 10 shots of the lead will make the weekend.
A little before midway through the second round, there were just 10 players in red-figures. Tied for fourth at one-under were seven players -- Moore (74), Rahm (73), Soren Kjeldsen (72) and Andy Sullivan (71), who had all begun second round.
Justin Rose, Phil Mickelson and Mathew Fitzpatrick, all 71 on first day, were yet to start second rounds.
Rory McIlroy, even on first day, was even through an action-packed nine with three birdies and three bogeys in second round.