Williams, playing her first competitive match since the US Open in September, cast off any doubts about her injured left knee with a hard-fought but convincing 6-4, 7-5 win over Italy's Camila Giorgi.
Temperatures soared at Melbourne Park, forcing players to reach for ice towels and water. Carla Suarez helped a ballboy off the court after he fell faint during her win over Viktorija Golubic.
Novak Djokovic, seeking a record sixth Australian Open title, and Roger Federer were also in action on Monday on a busy first day at the year's opening Grand Slam, along with Maria Sharapova.
But the 34-year-old, clad all in canary yellow, showed no sign of injury as she came through a testing match on Rod Laver Arena against Giorgi, the tournament's highest ranked non-seed.
"I haven't played a competitive match in a really long time so it was good for me to come out here and get through it," Williams said.
"I was able to stay in it and stay calm and that is what matters most."
But debate was dominated by a report which said 16 top-50 players over the past decade, including Grand Slam champions, had repeatedly been suspected of match-fixing without facing action.
Three suspect matches were at Wimbledon, and eight of the players under suspicion were due to take to the courts for the Australian Open in Melbourne, the BBC and BuzzFeed claimed.
Association of Tennis Professionals (ATP) chief Chris Kermode rejected any suggestion that match-fixing evidence had been covered up or ignored.
"And while the BBC and BuzzFeed reports mainly refer to events from about 10 years ago, we will investigate any new information, and we always do.
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