Brazil won the shoot-out by 7-6 after 120 minutes of play in ordinary and extra time.
Australia's Matildas and the host nation were all square at 4-4 when five-time world player of the year Marta stepped up to the spot.
But goalkeeper Lydia Williams made an excellent save, giving Katrina Gorry a golden opportunity to slot the game-winner.
Again it was the goalkeeper who stood tallest, with Barbara diving to her right to make a brilliant save to deny the 2014 AFC women's player of the year.
