After a slow start, the Blues were the first to trouble the scorers in the 12th minute.
Following a penalty, a shift to the right-hand side saw five-eighth Luisa Yaranamua take on the Queensland defence herself and muscle her way over the line.
Rueben Cherrington failed to convert, as the score was 4-nil.
Five minutes later, the hosts came within touching distance of the try-line, but a fifth-tackle grubber rolled over the dead ball area to hand possession back to NSW.
In the closing minutes of the first half, Queensland conceded another penalty - with ball-in-hand - in their own half allowing the Blues an opportunity to extend their lead before half-time.
The Blues did exactly that and again Yaranamua was heavily involved in the try - latching onto an offload from five metres out before throwing a pinpoint cut-out pass for winger Berry to score.
With the half-time whistle approaching, the Maroons were desperate to get on the scoresheet before the break, and they received a chance in the 29th minute after a NSW error in their own red zone.
Within a matter of seconds, the Queenslanders were able to cross the stripe through back-rower Sara Sautia on the left edge.
Second-row forward Zoe Cook converted from out wide as the siren sounded to leave Blake Cavallaro's side clinging to a 10-6 lead at the break.
The Maroons continued their momentum in the early exchanges of the second half, finding themselves in attacking position in the 33rd minute before Hannah Larsson charged at a gap in the defensive line to score untouched beside the posts.
Cook converted her second goal to give Queensland a 12-10 lead.
The ensuing 13 minutes of the match saw points at a premium as both sides made handling errors close to the line before NSW were presented a chance in the 45th minute with a scrum on their own 10-metre line.
Enter Teagan Berry.
Halfback Tayla Montgomery threw a long ball from the feed and, within two passes, it found the hands of Berry who outpaced her opposite winger and raced away for her second try.
Yaranamua took on the goal-kicking duties and successfully converted for a 16-12 lead.
The Blues then attempted to push their lead further with a minute remaining but the ball was kicked dead to give Queensland one more chance to score with seven tackles in hand.
NSW looked to be on their heels as the Maroons were tackled only metres from the try-line before the visiting side forced an error at the play-the-ball to seal the four-point win.
Yaranamua was named player of the match, in a fixture that marked the first representative state pathways fixture to be played since 2019 after last year's COVID-affected season.