Amanda Gutierres struck in the sixth and 13th minutes - a day after telling media she hoped to score two goals - at Suncorp Stadium to bring Australia undone in front of 47,501 fans on Thursday.
Caitlin Foord finished off a wonderful team goal in the 43rd minute but Atletico Madrid winger Gio rounded out Brazil's win in the 54th.
Olympic silver medallists Brazil were a constant danger on the counter attack and interim coach Tom Sermanni's back three was caught out on multiple occasions, while Australia looked disjointed in attack.
"Their pace and their aggression were a little bit better than ours early in the game, and we got punished for that," Sermanni said.
Gabrielle Jordao Portilho reacts after a goal from Brazil teammate Amanda Gutierres. (Dave Hunt/AAP PHOTOS)
Australia will attempt to turn things around, with Sermanni likely to rotate his suqad when they and Brazil lock horns again at Cbus Super Stadium on the Gold Coast on Sunday night.
In an at times spiteful clash, frustrations threatened to boil over, with Foord and Hayley Raso livid at Brazil's physical approach as the visitors ended up with 10 players after a late red card.
"The game was intense, was physical, but Brazil were ready for it," Gio said through an interpreter.Â
"It's a way Brazil like playing and it's trying to play this way and being offensive and trying to attack."
In her celebration match, retiring great Polkinghorne started and captained the team in her home town, marking her record 168th appearance.
She was celebrated pre-match with a guard of honour and substituted to a round of applause in the 63rd minute.
Emily van Egmond made her 150th appearance, while Winonah Heatley started as a defensive midfielder, and impressed, though Australia missed Katrina Gorry and Clare Wheeler.
Brazil winger Marilia was taken off on a stretcher in the 23rd minute, while goalkeeper Natascha was substituted in the second half, skipper Yasmim was stretchered off in the 74th minute and Fe Palermo hobbled off late.
Brazil going in for the kill 💥— Paramount+ Australia (@ParamountPlusAU) Amanda Gutierres has an early brace in just her 3�⃣rd cap for 🇧🇷 to silence Suncorp!#AUSvBRA is LIVE on Paramount+ pic.twitter.com/4whhyh0eCvNovember 28, 2024
Brazil took the lead when Vitoria Calhau launched a long ball over the top and Polkinghorne couldn't clear it.
The ball dropped to Palmeiras striker Gutierres, who rounded Mackenzie Arnold and coolly scored.
Seven minutes later, Gomes burst forward and cut the ball back to Gutierres, who leathered a wonderful first-time left-footed strike past Arnold.
Australia scored when Heatley launched a well-weighted long ball to the tireless Ellie Carpenter, who bodied her opponent, then turned her inside out before squaring it.
Van Egmond left the ball for Foord, who turned on a dime and finished with aplomb.
Ellie's pass � EvE's fake 😮�💨 Caitlin's finish 💥— CommBank Matildas (@TheMatildas) Just what we needed before half time ��� @10FootballAU #AUSvBRA #Matildas #ThankYouPolks pic.twitter.com/jKGgxAar6pNovember 28, 2024
Australia burned early second-half chances, then Gio forced Alanna Kennedy into a turnover, with Gomes nudging the ball forward for the exciting attacker to score.
Brazil went down to 10 when Calhau received her second yellow card in the 87th and Freier was denied by an extraordinary save from Lorena at the death.