Their 4.3 (27) to 3.6 (24) victory in the bottom-of-the-ladder clash at Swinburne Centre on Friday comes at the halfway mark of the 11-round season after five straight losses.
It is also their first win under first-year coach Sam Wright since parting ways with Steve Symonds in November.
Symonds led Collingwood to finals action in each of his first four seasons, but a disappointing 11th-placed finish in 2023 cost him his post.
Wright said he was thrilled for the Magpies to finally register their first win of the season.
Sam Wright has notched his first AFLW victory as Collingwood coach. (Rob Prezioso/AAP PHOTOS)
"We have a saying and that's unity through adversity," he said after Friday's match.
"It's funny in footy. It gets to that last 40 seconds of a game and you're still not sure and it starts to tick down.
"You take a mark and just that moment before you win is probably the best moment in footy."
The Magpies' win came at a cost, with Mikala Cann, returning from a one-match suspension, subbed out with a shoulder injury.
Meanwhile, the Suns remain the only winless team left with five losses and one draw after making their first finals appearance last year.
"We've had three games now where we've drawn, lost by a point, lost by three points," Suns coach Cam Joyce said.
"You take a kick in all those and suddenly you're three and two (win-loss) and everyone's saying how well you're going.
"The truth is somewhere in the middle there."
Brittany Bonnici, back from a calf strain, was inspiring for Collingwood and shook off a shoulder complaint to finish with 27 disposals and eight clearances.
Bonnici was well supported by usual stars Ruby Schleicher (one goal), Sarah Rowe and Tarni White (two goals).
Suns superstar Charlie Rowbottom led the game with 30 disposals, and Lucy Single stood out with nine clearances, but the duo could not lift their team over the line.
Charlie Rowbottom was prolific for the Suns, racking up 30 disposals against Collingwood. (Dave Hunt/AAP PHOTOS)
Gold Coast brought the heat early but could not convert their on-field dominance to the scoreboard, leading two points to none at the first change.
All-Australian defender Schleicher went full-throttle in the opening minute of the second term and launched from the inside-50 line to get Collingwood on the scoreboard with the first goal of the match.
Jamie Stanton replied for the visitors, but her goal was chalked off after the newly introduced smart-ball technology detected the Sherrin had been touched.
A free kick and 50-metre penalty paid against Rowbottom gifted White a major, but Gold Coast finally found reward through a Georgia Clayden goal to reduce the deficit to five points at half-time.
White extended Collingwood's lead with her second, but Stanton kicked truly, before Suns skipper Tara Bohanna put her side ahead by two points at the final change.
But Collingwood were relentless and Imogen Barnett, from just in front of goal, won the ball from the ruck and scored the eventual match-winner.
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