The American top seed used her powerful serve to good effect as she raced past experienced Slovak Daniela Hantuchova on another hot Melbourne day, 6-3, 6-3 in 80 minutes.
Williams, bidding for a sixth Australian Open crown, now faces either former world number one Ana Ivanovic or 2011 US Open champion Samantha Stosur for a place in the quarter-finals.
"It was a tough match. Daniela is a great opponent so I'm really happy to come out with the win," said Williams.
Hantuchova, ranked 33, was never going to be an easy opponent and she had her chances with six break points. But Williams fired down aces at crucial times, with eight in the first set alone.
The victory set a new landmark for the American veteran, who is gunning to match the achievement of Chris Evert and Martina Navratilova in winning her 18th Grand Slam.
Beating Hantuchova was her 61st win at the Australian Open, surpassing the previous record set by Margaret Court.
Williams, who made her Australian Open debut in 1998, also drew alongside Open-era record-holder Lindsay Davenport in playing 69 singles matches at Melbourne Park.
With a career-best 11 titles last year, the 32-year-old appears to be getting better with age and she has no plans to slow down.
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