The Wellingtonian helped her side post a competitive 228 for six with a superb undefeated 74 in the opening Rose Bowl match in Queenstown yesterday.
She then turned destroyer with the ball, nicking out talented Australian opener Shelley Nitschke for 51 and dismissing the dangerous Sarah Elliott before she really got going.
Australia clawed its way back into the match, Jess Cameron top-scoring with 68 and Ellyse Perry chipping in with a valuable 27.
The pair put the visitors on course for victory but Amy Satterthwaite tilted the balance back to the home side when she enticed both batsmen into making mistakes.
Australia needed 14 runs from the last over with two wickets in hand when White Ferns captain Aimee Watkins threw Devine the ball.
The previous 99 overs had been kind to Devine but her luck deserted her at a crucial time.
Julie Hunter got an inside edge for four off the last delivery to seal a dramatic two-wicket win and give the visitors a 1-0 lead in the three-game series.
While it was heartbreaking watching the ball trickle across the boundary rope after a false stroke, White Ferns coach Gary Stead believes his side has closed the gap since losing all five one-dayers in Australia earlier this year.
"We were thumped over there, really," he said.
"But if that inside edge would have gone to a fielder we would have won the game today.
"That's the luck of the draw at times.
"We've had some close games which have gone our way, and this one didn't.
"But we'll look where we can improve and there are still areas we can get much better in," he said.
Earlier, the White Ferns made a poor start, Otago duo Katey Martin (3) and Suzie Bates (8) getting out cheaply.
Perry claimed both scalps.
Auckland's Victoria Lind held the innings together with a patient knock of 68.
But the carnage continued at the other end with Satterthwaite (9) and Sara McGlashan (0) not bothering the scorer much.
Devine and Nicola Browne combined in a undefeated seventh-wicket stand of 69.
"I thought 228 was a reasonable score if we bowled well and unfortunately it came down to the last ball and it got French cut for four," Stead said.
The next game is in Invercargill on Saturday.
