With scores level at the main break, the Swans produced a four-goal third-quarter flex to set up an 8.2 (50) to 4.11 (35) victory in front of 5489 fans at North Sydney Oval on Friday night.
Swans co-captains Chloe Molloy (two goals) and Lucy McEvoy (one goal, 17 possessions) led from the front as the hosts overwhelmed their opponents with quick ball movement.
Ball magnet Laura Gardiner (23 disposals) was outstanding in the contest, well-supported by Sofia Hurley (15) and Breanna Tarrant (nine intercept possessions).
The win by Sydney, in their third AFLW season, gives new Magpies coach Sam Wright much to think about.
Former North Melbourne utility Wright was handed the reigns after Collingwood parted ways with Steve Symonds in November following a disappointing 11th-placed finish in 2023.
Brit Bonnici (24 touches) was a shining light for the Magpies while skipper Bri Davey watched from the sidelines after failing to prove her fitness following an off-season ankle reconstruction.
Sabrina Frederick also impressed in the ruck for the Magpies and took 25 hit-outs to 13 against All-Australian star Ally Morphett, who was returning from a foot injury.
Molloy gave Collingwood debutant Mureiann Atkinson a baptism of fire after marking directly in front of goal to kick the opening major of the AFLW season.
Grace Campbell replied quickly for the Magpies but McEvoy slotted another to build a four-point lead at the first break.
Collingwood rallied to dominate territory in the second term but wasted chances in front of goal, kicking 1.4 to one to level the scores.
Campbell momentarily stole the show after Sydney's Tanya Kennedy sent the ball with a thundering kick directly into the Magpies forward's face from point-blank range.
The 28-year-old was able to return to play.
But Collingwood's Tarni White faces a nervous wait after a high bump left Maddy Collier, in her first game since rupturing her anterior cruciate ligament last year, concussed.
Atkinson was also ruled out with a concussion when her head clashed with Molloy's on the other end just minutes after White tackled Collier.
Molloy shrugged off the collision to slot her second goal of the evening, helping to launch Sydney to a 23-point lead in the third term.
Wright shuffled the magnets for the final quarter and sent full-back Stacey Livingstone forward.
The move paid immediate dividends, with Livingstone scoring her first goal in 67 matches before Alana Porter reduced the margin to 10 points.
But an after-the-siren goal from Bec Privitelli restored Sydney's margin to 15 points.
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