Top seed Djokovic, untroubled so far as he seeks a sixth Australian Open title, takes on Italian 28th seed Andreas Seppi having beaten him in all 11 of their previous meetings.
Williams resumes her pursuit of a seventh crown at Melbourne Park against Russia's Daria Kasatkina after fifth seed Maria Sharapova takes on 22-year-old American Lauren Davis.
Djokovic will be happy to be back on court after his serene progress was interrupted in his post-match media conference on Tuesday when he was forced to deny allegations in an Italian newspaper about match-fixing in 2007.
He will be wary though as Seppi beat Roger Federer at exactly the same round of last year's Australian Open.
Federer, the 17-times grand slam champion, meets 27th seed Grigor Dimitrov, who was once labelled "Baby Federer".
He will look to record a landmark 300th grand slam win, becoming the first man in history to achieve the feat.
Women's fourth seed Agnieszka Radwanska, still searching for a first grand slam title, faces Puerto Rico's Monica Puig while Japan's Ken Nishikori, seeded seventh, starts things off on the Margaret Court Arena against Spain's Guillermo Garcia-Lopez.
A day after Lleyton Hewitt's final bow, one of Australia's big new hopes, Nick Kyrgios, takes on sixth seed Tomas Berdych in what promises to be a raucous night session.
(Reporting by Shravanth Vijayakumar in Bengaluru; editing by Martyn Herman)
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