The inaugural version of the women's tournament was hosted at Wembley, with Tottenham's very own Richarlison watching on from the stands.
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Sarina Wiegman's stars gained progression to the spectacle thanks to their Euros triumph last summer.
Their opponents Brazil won the South American equivalent, the Copa America Femenina, to set up the match at Wembley.
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England, who are now 30 games unbeaten under Wiegman, have already tested success at the home of English football, and Ella Toone was back amongst the goals there once again.
The Manchester United star capped off a lovely, flowing move with a strong finish from Lucy Bronze's pass.
Her fellow United teammate also impressed under the lights, pulling off a superb save in the second half to deny Geyse.
The Lionesses were minutes away from victory, but a second half stoppage time goal from Andressa sent the match to a penalty shootout.
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Both goalkeepers made fine saves during the spot-kicks, with Chloe Kelly, who scored the winner against Germany in the Euro 2021 final, proving to be the hero once again with the winning penalty.
Spotted in the crowd at Wembley was Brazilian men's star Richarlison, who is approaching a return from injury at Spurs.
A total crowd of 83,132 were in attendance at the Home of Football to watch England win the title.
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Such a number makes the match the fifth most attended official women's game, with four of those coming in the last 13 months.
Before the game, the Lionesses' record goal scorer Ellen White was honoured on the pitch at Wembley thanks to her 52 goals in 113 appearances.
The men's version of the Finalissima was also held at Wembley last year as Argentina beat Italy 3-0, with Lionel Messi being the star of the show.