Former winners Jack Nicklaus, Gary Player and Tom Watson, drove off the first tee as honorary starters in the traditional ceremonial launch to the year's first major tournament.
Conditions were warm with temperatures expected to reach 87 degrees Fahrenheit, overcast but dry although rain is forecast for later in the week and could impact the schedule.
Canada's Mike Weir, the 2003 Masters champion, was the first player in the field to get under way, playing in the opening pair with American Kevin Na.
Na is one of 18 players in the field from the new Saudi-backed LIV Golf League, which is locked in bitter legal battles with the established PGA Tour.
This Masters is the first time that the top-ranked players from the PGA Tour and LIV Golf are in the same field at Augusta National.
The PGA Tour has banned LIV players, with their US court fight set to begin early next year.
Just hours before the start, a tribunal in London ruled against LIV players in their dispute with the DP World Tour, formerly the European Tour.
The arbitration panel ruled that the DP World Tour was entitled to sanction the players for appearing in LIV events without authorization.
The full impact of that decision will unfold in the coming weeks but players have insisted their focus this week is on the battle for the green jacket.
World number one Scottie Scheffler is looking to become just the fourth player to win back-to-back Masters.
The American world number one is the bookmaker's favorite to slip into the famous green jacket when the four rounds are complete on Sunday evening.
Scheffler has been a model of consistency over the past 14 months, which has seen him win six PGA Tour titles, most recently at the Players Championship in March.
Only Nicklaus, Nick Faldo and Tiger Woods have achieved successive victories in the Masters.
Woods will also be out on the pristine course later on Thursday in what he has speculated could be one of his last appearances in the tournament he has won five times.
Dampening expectations
A victory for Woods would see him equal Nicklaus' record of six triumphs in the Masters, but hampered by a series of injuries, the 47-year-old has been dampening expectations.
"I don't know how many more I have in me," Woods said. "So just (have) to be able to appreciate the time I have here and cherish the memories."
Last year's runner-up, Northern Irishman Rory McIlroy, is hoping to finally complete his career Grand Slam with a long-awaited Masters triumph.
McIlroy has been a leading supporter of the PGA Tour, for whom a nightmare scenario would be the sight of a LIV rebel celebrating in the green jacket - not an entirely fanciful notion.
Australian Cameron Smith, the reigning British Open champion, tied for third at Augusta last year, while fellow LIV Golf player Brooks Koepka has won four majors and Dustin Johnson, who won LIV's first season, triumphed in Augusta three years ago.
The PGA Tour has a much deeper list of contenders with world number three Jon Rahm of Spain, 2015 winner Jordan Spieth and two-time major winner Justin Thomas among those in with a chance.
