The 37-year-old American, who lost to sister Serena in the final last year, enjoyed great success on the Grand Slam stage in 2017 but the in-form Bencic underlined her credentials as a future world No 1 with a polished performance - securing a 6-3 7-5 victory in one hour and 53 minutes.
Bencic, back to full fitness after two years impacted by injury, came into the new season on the back of a 15-match winning run and partnered compatriot Roger Federer to Hopman Cup success earlier this month.
Bencic, a former top-10 player at 18, started the stronger of the two on Rod Laver Arena and made a mockery of her world No 78 ranking to secure the first break of the match in the seventh game before a rain delay forced an interruption to the encounter.
The Swiss 20-year-old held serve from deuce on the resumption before she secured a second break on her way to the opening set.
The hard-hitting pair exchanged early breaks in the second set and despite Bencic seeing two break points at 3-4 go begging, she showed immense composure in the final game to break Williams' serve to secure her first victory over her American opponent and book a second-round meeting with qualifier Luksika Kumkhum.
There was further disappointment for American hopes with the exits of US Open champion Sloane Stephens and CoCo Vandeweghe to Zhang Shuai and Timea Babos respectively.
Stephens, who suffered a torrid denouement to the tennis calendar last year, remains without a win since her surprise triumph at Flushing Meadows and despite an encouraging start, she fell to a 2-6 7-6(4) 6-2.
The US Open semi-final spots were all taken by American players in New York but after 10th seed Vandeweghe, coached by Australian Pat Cash, lost to fellow big-hitter Timea Babos 6-7(4) 2-6 in one hour and 46 minutes, only one remains - Madison Keys.
Pre-tournament favourites Caroline Wozniacki and Elina Svitolina both stormed to comprehensive first-round victories against Mihaela Buzarnescu and Ivana Jorovic respectively.
Wozniacki, world No 2, eased to a 6-2 6-3 success over her Romanian opponent in one hour and 11 minutes while Svitolina, Brisbane International title holder, proved too strong for Ivana Jorovic 6-3 6-2.
French Open champion Jelena Ostapenko needed a second-set comeback to progress past veteran world No 93 Francesca Schiavone 6-1 6-4 and earn a second-round encounter with Ying-Ying Duan.
The Latvian world No 7 breezed through the first-set but after Schiavone initially threatened to force the match into a deciding set, Ostapenko recovered to win five successive games to record victory in one hour and 14 minutes.
Kaia Kanepi defeated 24th seed Dominika Cibulkova, a former finalist in Melbourne, in comprehensive fashion 6-2 6-2 to set up a match with Monica Puig - who ended the campaign of home favourite Sam Stosur.
Puig, Olympic gold medallist in Rio, recovered a set and break deficit to force a second-set tie-breaker which the Puerto Rican took after saving a match point and took full advantage of the change of momentum to progress 4-6 7-6(6) 6-4.
Source:Skynews
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