Hard-running Spanish scrapper Pedro Martinez loomed as an opponent who could drag out Monday night's first-round clash at Rod Laver Arena.
But a scintillating Djokovic was having none of it, pulling out all his tricks with a combination of precision and power to claim a 6-3 6-2 6-2 victory, his 100th at the Australian Open.
Djokovic has also notched 102 wins at Wimbledon and 101 at Roland Garros.
"I mean, what can I say? I like the sound of it," he said.
"Centurion is a nice feeling.
"I'm blessed to be still playing, honestly, at this level. Making another win tonight is obviously a dream come true."
The 38-year-old, at his 21st Open, is chasing a record-extending 11th Melbourne Park title.
World No.4 Djokovic has been adamant he isn't putting pressure on himself to surpass Margaret Court for the outright most singles slam titles, amid Carlos Alcaraz and Jannik Sinner's recent dominance.
Pre-tournament, Djokovic noted he was lacking the "juice" in his legs to go with the world No.1 and No.2 late in slams, and would have to take care of his body to let him compete deep in the tournament.
Monday night's match was exactly the type of ruthless affair needed if the super Serb is to do just that - with Djokovic hitting 49 winners and 14 aces.
"It always feels good at the beginning of the tournament, let's see how I progress," he said.
"Tonight's performance was definitely great - I cannot complain about anything.
"I served very well and obviously it's always a challenge to kickstart the competition and a tournament with the right note and sending the right signal not just to yourself but to all your opponents watching you play."
Djokovic had skipped his usual Adelaide International warm-up after a setback, but was irresistible as he quickly claimed a double break and raced away to a 3-0 lead in the first set.
He only needed 30 minutes to claim the second set and put the contest firmly in his control.
The Serb was stretching out his left leg after the set, while he had taping on his right shoulder - but showed no ill effects.
He flashed a confident grin and swaggered back to his baseline as he ripped a scintillating forehand winner past a helpless Martinez early in the decider.
The world No.71 applauded his opponent after a delightful lob minutes later.
The Spaniard dug in but Djokovic was inevitable and at 2-2, he broke Martinez's serve and never looked back.
Djokovic will next face Italian qualifier Francesco Maestrelli.
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