Former Western Sydney forward Bryleeh Henry and midfielder Leticia McKenna produced City's crucial goals at Wanderers Football Park on Sunday.
But their strikes were overshadowed by forward Chinaza Uchendu after she shoved Amy Chessari to the ground before lashing out at Alana Cerne.
Uchendu then got into a scuffle with Western Sydney players and had to be held back by teammates before referee Izzy Cooper handed her a red card in the 17th minute.
As she walked off the pitch, the 28-year-old stuck up her middle finger to the crowd.
Earlier, Canberra United cemented their position in the competition's top six after a horror mistake by Adelaide United's goalkeeper Ilona Melegh led to a 3-2 victory at McKellar Park.
Without inspirational forward Michelle Heyman because of Matildas' duties, Emma Hawkins stepped up for the home side, assisting the opener and scoring their third goal.
Hawkins also pressured defender Matilda McNamara to loft a pass towards Melegh, but the teenager couldn't control the ball, which rolled into the net and sent Canberra 2-1 up.
Eight minutes later, Hawkins landed the knockout blow when Bethany Gordon found the 24-year-old, who fired it into the top right corner.
Victory means Canberra (30 points) leapfrog their opponents into third while also dealing Adelaide (30 points) a hammer blow to their premiership plate aspirations.
With Melbourne (37) beating the 10th-placed Wanderers, they are now in the box seat to claim their third consecutive plate, sitting six points clear with two rounds remaining.
Gordon drew first blood but Adelaide equalised when an open Sarah Morgan calmly slotted home.
Canberra took the lead through Melegh's own goal in the 69th minute, before Hawkins netted, although Adelaide substitute Sian Dewey hit the ball from distance into the bottom left corner in injury time.
Seven minutes after Uchendu's red card in Sydney, McKenna scored after a superb ball from Danielle Turner, before Henry added City's second on the stroke of halftime.
In the 53rd minute, 17-year-old Talia Younis produced the strike of the match when she whacked the ball from way outside the box, and it nestled into the top right corner, but Melbourne held strong to secure a tense victory.