Langer, a twice champion at Augusta National, recorded three birdies in breezy sunshine to reach the turn in a flawless three-under-par 33, level with American Steve Marino who had completed six holes.
The 52-year-old Langer, who plays most of his golf on the seniors Champions Tour, narrowly missed out on a fourth birdie when his attempt from 10 feet at the par-four ninth slid past the left edge of the cup.
Wearing a bright red shirt and black trousers, the ice-cool German was warmly applauded by the gallery crammed behind the green as he made his way up the hill to the 10th tee.
Golfing great Tom Watson, an eight-times major winner, was among a group of three players at two under after six holes.
The eyes of the golfing world, however, will be firmly fixed on disgraced world number one Woods when he tees off in the second-to-last group of the day.
The 14-times major champion, who has won the Masters four times, has not competed since winning the Australian Masters on Nov 15 following stunning revelations about his serial philandering.
With a record television audience likely to be watching his first competitive round in one of sport's biggest events this year, Woods will play the first two rounds in the company of South Korean KJ Choi and American Matt Kuchar.
Asked earlier this week if he felt ready to clinch his 15th major title after a lengthy break, Woods replied: "Nothing's changed. I'm going to go out there and try to win this thing."
The 34-year-old will be bidding to become the first player since World War Two to launch his season with a major victory since fellow American Ben Hogan clinched the 1953 Masters.
In other high-profile groupings, in-form Ernie Els has been paired with American Anthony Kim and Japan's Ryo Ishikawa while holder Angel Cabrera of Argentina is playing with South Korean An Byeong-hun and American veteran Jim Furyk.
Three-times major winner Padraig Harrington of Ireland will set off in the company of British Open champion Stewart Cink and South African Charl Schwartzel. There is a chance of rain in the late afternoon on Thursday with cool, overcast weather forecast for Friday and sunny conditions expected for the weekend.
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