Williams overcame a sluggish start to overpower Italy's Sara Errani 6-3, 6-2, as top seed Caroline Wozniacki, Maria Sharapova and Francesca Schiavone all struggled to impress.
Wozniacki took 1hr 40min to see off Gisela Dulko 6-3, 6-4 and Sharapova struggled with her serve before beating Thai veteran Tamarine Tanasugarn 6-1, 6-3 at Rod Laver Arena.
Meanwhile French Open champion Schiavone lost the first set to Arantxa Parra Santonja before eventually winning 6-7 (4/7), 6-2, 6-4.
Williams, the United States' best hope in the absence of sister Serena, the current champion, risks being underdone after not playing a WTA tournament since the US Open.
She has been something of an under-achiever at the Australian Open, reaching the final once, in 2003, but often falling early to unheralded opponents.
She lost in the 2010 quarter-finals to China's Li Na and went down in the second round in 2009 to Carla Suarez Navarro of Spain.
Earlier Wozniacki, under pressure to claim a maiden Slam title to convince critics she is a deserving women's number one, laboured to subdue 52nd-ranked Dulko, who made 38 unforced errors during the match.
And former champion Sharapova admitted she had room for improvement after her win over 33-year-old Tamarine. The 2008 winner lost her opening service game but hit back to win the next six games.
The Russian broke again in the first game of the second set before going off the boil, dropping the next three games to go 3-1 down before once again recovering strongly.
Sharapova has already improved on last year's performance, when she was shocked in the first round by fellow Russian Maria Kirilenko.
Elsewhere fifth seed Schiavone lost the opening set as Parra Santonja blazed away with a succession of clean winners. But the gritty Italian attacked in the second, breaking twice to level the match at one set apiece.
Schiavone broke to make it 5-4 in the decider, but she then faltered when serving for the match, giving the break straight back to the Spaniard.
However, Parra Santonja cracked while serving to stay alive, handing the first round tie to a relieved Schiavone 6-7 (4/7), 6-2, 6-4.
Other seeded players to progress were France's 15th ranked Marion Bartoli, who trounced Italian Tathiana Garbin 6-0, 6-0, Estonian Kaia Kinepi (20), who beat Magdalena Rybarikova 2-6, 6-4, 6-3 and Slovakia's Dominika Cibulkova (29), a 6-2, 6-7 (4/7) 6-4 winner over German Angelique Kerber.
China's Li, who reached last year's semi-finals and is fresh from victory at the Sydney International, went through against Sofia Arvidsson of Sweden.
The women's draw has been blown wide open by the injury withdrawal of five-time champion Serena Williams. Belgium's Kim Clijsters is the favourite but faces a tough first-round assignment against 2009 finalist Dinara Safina.
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