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Canberra: The Indians were absolutely cruising in their run chase until the 212-run partnership between Shikhar Dhawan and Virat Kohli ended when the left-hander fell for 126 in the 38th over.
Dhawan's wicket was the first in a barely believable collapse of 9-46 in 58 minutes that somehow handed Australia victory and a 4-0 series lead.
The fortunes of Kane Richardson fluctuated as much as this match did, but he returned in the final overs to trigger a collapse that sparked Australia's victory.
Having conceded just three runs from his first two overs, the right armer was hit for 30 from his next two and began his final spell with figures of 1-52 from six overs. He then ripped out four Indian batsmen in as many overs, finishing with career-best figures of 5-68 in a match-winning performance.
Earlier, Aaron Finch's seventh one-day international century laid the platform for Australia's monster total of 8-348, the Victorian sharing a 187-run opening stand with the returning David Warner (93 from 92 balls).
In chase, hundreds to Kohli and Dhawan tonight bring to five the number of Indian century-makers in this series, none of which have come in victories.
Their 212-run partnership appeared to be steering India to a comfortable victory, but the dismissal of Dhawan and then Kohli a short time later helped to hand Australia the victory.
Kohli made it one-day hundred No.25 in a controlled innings that may not have steered his side all the way to the target but took a sizeable chunk out of it.
Brief scores
Australia - 8 for 348 (Finch 107, Warner 93, Smith 51, Ishant 4-77)
India - 323 (Dhawan 126, Kohli 106, Richardson 5-68)
Result - Australia won by 25 runs
MOM - Kane Richardson (Australia)
