The clash against Hantuchova began a tough day for the world No.1 who is also scheduled to partner her sister Venus in doubles.
Only minutes before Williams won through, German ninth seed Angelique Kerber became the first woman into the fourth round of the Open thanks to a straight-sets victory over American Alison Riske.
Kerber said she had to force herself to focus on her game and not the weather.
"I'm just happy to have won and got off the court before it became really hot," she said.
"I was trying to concentrate on each point and forget about the sun."
Kerber won 6-3 6-4 to reach the same point in the championship as last year.
Also through, and also in straight sets, is Italy's Flavia Pennetta.
The 28th seed accounted for Germany's Mona Barthel 6-1 7-5, getting the job done in 74 minutes.
A top temperature of 44 degrees is forecast for Melbourne on Friday.
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