Hoffman strung together six birdies on the back nine yesterday and went off at 3.01pm BST alongside England's Chris Wood and Japan's Yuta Ikeda.
William McGirt meanwhile, having shot 69 on his first effort round Augusta, was in the very first group, hoping to avoid the worst of the wind with his early slot.
As usual, the final groups are chock full of big names with Jordan Spieth, Phil Mickelson and Justin Rose all going off in the last three tee-times, the latest group starting at 7.03pm UK time.
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6pm BST: Charley Hoffman reaches the turn in 38 and the American will now be looking over his shoulder with concern.
Just a shot behind is Sergio Garcia, after he slides home from seven feet at the ninth to reach the turn in 33.
Rory McIlroy is now one under through seven and sits in fourth on the leaderboard.
Sergio Garcia is now just one-shot off the lead
5.30pm BST: Rory McIlroy is on the move now. After bogeying the first and the third for the second day in a row, he knocks in birdie putts at five and six to move within four shots of the lead.
And the gap is only that small because Hoffman has had a wobble. After bogeying six and seven, he makes a six at the par-5 eighth and all of a sudden, the pressure of leading is starting to tell.
Charley Hoffman found out on Friday that leading the Masters is not an easy task
5pm BST: Rory McIlroy can't catch a break this week.
After a birdie at 2, the Northern Irishman two-putts from 11 feet on the third and is back to +1.
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Elsewhere, a three-putt at 6 from leader Charley Hoffman sees him move back to -7, still four ahead of William McGirt and Sergio Garcia.
Rory McIlroy can't get going this week
4.30pm BST: Sergio Garcia is on fire!
The spaniard drained a 20-footer at third for his third birdie in his opening three holes.
Elsewhere William McGirt has lost his share of second after missing the green and then taking two goes from 15 feet.
Lee Westwood Westwood has given back his birdie at the second with a missed par save from six feet at the next.
Sergio Gracia has birdied his first three holes
4pm BST: Serg-i-o! Garcia, one of the great wind players with his low ball-flight, was bogeyless yesterday in a round of 71 and has started even better today.
After becoming one of the few men today to birdie the first, the Spaniard repeats the feat with a four at the par-5 second.
His playing partner Lee Westwood, he of five straight birdies yesterday, matches him at the second getting back the shot he dropped at the first.
Two of the greatest golfers never to have won a major championship are lining themselves up.
Sergio Garcia made a strong start to his round on Friday
3.30pm BST: Overnight leader Charley Hoffman is out on the course and has made the first look a lot easier than Danny Willett did, two-putting from 50 feet for par.
The Englishman meanwhile drops another shot at the fourth hole by three-putting from just 25 feet.
It's been a tough start for the defending champion, who might not even make the weekend at this rate – he's two shots off the cut line at the moment.
Charley Hoffman puts from 50 feet for par
3pm BST: Proof that being defending champion means nothing as Danny Willett records a QUADRUPLE bogey on the opening hole.
His score of 73 yesterday was respectable – including a double bogey at the first – but the hole has had another bite at him today.
A wayward drive and scenic trip to the green sees him card an unlikely eight. That's got to sting.
Danny Willett had a horror show of a first hole, jumping from 1 to 5
2.30pm BST: Jason Dufner was one of those who dropped shots on the run home last night, drifting from three under par to one.
But the 71 he signed for was still a good platform for Friday. If only he'd started well today. The American bogey 18 last night and records a double the first this morning.
Only two men are under par so far today – McGirt and Ryan Moore who knocks his putt in for birdie at the par-5 second.
Jason Dufner had a good Thursday but started poorly on Friday morning
2pm BST: McGirt strikes back! Okay – that's never going to be a movie, is it. Well anyway, he has done so with a birdie putt at the second and chipping in from the bunker at the fourth.
Elsewhere, Ross Fisher isn't going anwhere fast. He was going nicely at -1 yesterday before chipping into the water from the back of the green at the eighth.
He carded a 76 and it isn't getting better today as the Englishman has opened with a double bogey.
William McGirt had an up and down start to the day
1.30pm BST: The early tee-time should suit McGirt but it isn't proving as much so far.
The received wisdom is that the wind gets stronger as the day goes on so if the American can get round without too much trouble, he could see the field drift backwards as Friday goes on.
It's not a great start though as he misses the first fairway, the first green and can't make his 15-foot par putt.
Hoffman's lead just got bigger and he's probably still in bed.
1pm BST: It's not very warm but it is at least sunny in Augusta today.
But the bad news for the golfers is it is quite breeze and the wind is expected to stiffen.
William McGirt is out with Rod Pampling in the first group.
McGirt has only played one round of competitive golf at Augusta before – yesterday – and the 37-year-old signed for a 69, one of only two players to break 70.