Chasing 230 on the final day of the four-day match on Monday, Victoria reached a comfortable 200 for three wickets before losing five wickets for a meagre 28 runs.
It was left to tailenders Andrew McDonald (16 not out) and Mick Lewis, who did not score, to defy the New South Wales bowlers and edge their side over the line.
The win gave Victoria six points, taking them to 14 points from four matches the same as Tasmania.
New South Wales remain fifth, with eight points, in the six-team ladder.
Victoria's late palpitations came after Jonathan Moss (63) and David Hussey (50) smacked 16 fours and three sixes between them in a sparkling fourth-wicket stand of 106.
Openers Jason Arnberger (41) and Matthew Elliott (33) were also in grand touch as Victoria launched their run chase in positive fashion.
New South Wales pace pair Stuart Clark (4-52) and Matt Nicholson (2-55) were both on target.