The loss means Williams bid to equal the all-time Grand Slam titles mark of 24, set by Australian Margaret Court, will have to wait until at least the French Open in May.
While Williams struggled to hit her targets throughout, her fighting spirit was never in doubt as she staved off a quicker defeat in the second set by breaking Wang as she served for the match at 5-4.
Speaking to media after her second round win on Wednesday, Wang said that she would be studying Williams' form and looking to improve upon the result of their previous meeting.
And this time she said goodbye much earlier.
Former Wimbledon champion Ivanisevic is one of only four ATP players to have served over 10,000 aces, and he joined Djokovic's coaching team past year. I just care about try to keep going, keep enjoying my tennis career.
Djokovic will meet another Japanese player in Yoshihito Nishioka, who knocked out British 30 seed Dan Evans in straight sets, for a place in the fourth round.
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Wang, who made just 20 unforced errors, had faced Serena in the US Open a year ago, but went down to the former champion 6-1, 6-0.
Djokovic is seeking to become only the third man to win eight or more titles at the same Grand Slam after Rafael Nadal (12 at Roland Garros) and Roger Federer (eight at Wimbledon).
There was to be no upset, however, as Nadal set up a second-round clash with either Argentina's Federico Delbonis or Portugal's Joao Sousa. Wang took the only break she needed in love with a simple forehand storage victor who finished 5: 4.
We take a closer look at the 33-year-old as he prepares for another match in Melbourne.
"I'm way too old to play like this at this stage of my career", she explained.
"You have to accept them and embrace the fact that, I guess, you're going to be challenged on different levels, not just by your opponent, but also the conditions".
Nadal, in a pink sleeveless shirt and matching shoes, was in total charge against the world number 73 Dellien, storming to a 5-0 lead in the opening set before the Bolivian held serve, then against the odds broke, before the Spaniard served out the set.