Without the retiring Alyssa Healy, and after dropping vice-captain Tahlia McGrath, Australia were bowled out for 133 in the series-opening Twenty20.
The tourists were then 1-50 when rain set in after 5.1 overs, taking a 21-run victory on DLS when umpires eventually called the fixture.
Australia's defeat was their first at home since early 2024, while their 133 was also the lowest score they've been bowled out for in a T20 in almost six years.
Sent in by India, Australia lost wickets at regular intervals and were unable to build momentum at any stage.
Georgia Wareham top-scored with 30, but Australia were never really able to take charge of the innings as India seamer Arundhati Reddy claimed 4-22.
After Australia were 2-27 early, Phoebe Litchfield (26) and Ellyse Perry (20) briefly threatened to take the game away from India.
But both were caught trying to take the bowling on, prompting a collapse from 2-67 to all out inside 18 overs.
Shafali Verma (21) then put India on top early in the chase, thumping two big sixes before being caught on the boundary pulling Molineux just before rain began falling.
India have not won a bilateral series in Australia in a decade, but the three T20s have much more riding on them with a World Cup in the format in June.
And with Australia's trophy cabinet now void of a T20 or ODI World Cup crown, selectors made several momentous calls in Sydney.
Besides McGrath, veteran seamer Megan Schutt and the hard-hitting Grace Harris were also left out.Â
Healy is also not in Australia's squad for the T20 series with an eye ahead to the World Cup, but will return for the ODIs and Test later over the next month.
Still, it was McGrath's omission that was the most notable on Sunday night, dropped for the first time since making a triumphant return to the side in the 2021-22 Ashes.
The 30-year-old McGrath looked poised to eventually take over from Healy as captain until recently, having deputised for her on 15 occasions.
But a difficult 2025 prompted officials to instead opt for Molineux as skipper, with Ashleigh Gardner joining McGrath as vice-captain in the squad.
Nicola Carey was selected in McGrath's place on Sunday night, scoring 12 after being called upon for the first time since knocking back a national contract in 2023.
The allrounder has spoken at length about wanting to prioritise more time training at home when she made the call, having felt her game plateau as a fringe player for Australia.
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