Six-time world player of the year Marta scored a record 17th World Cup finals goal to clinch Brazil’s place in the last 16 with a 1-0 win over Italy, who topped Group C on goal difference.
The 33-year-old Brazil legend’s nerveless, second-half penalty saw her become the all-time leading scorer at men’s or women’s World Cups, surpassing retired Germany striker Miroslav Klose.
Italy, who had already qualified, went close twice through Juventus’ Barbara Bonansea in the first half, but faded after the break in Valenciennes.
But an experienced Brazil side, who clipped the bar through Andressinha’s fine second-half free-kick, narrowly missed out on second spot as Australia beat Jamaica 4-1 to pip Vadao’s side on goals scored.
The South Americans now look set to face hosts France in the next round in Le Havre on Sunday, unless a relatively unlikely combination of results later this week puts them on a path to meet Germany on Saturday instead.
As group winners, Italy will play against a third-placed team in the last 16, with Nigeria or China their most likely opponents.
Brazil, winners of the past three Copa Americas, have now reached the knockout stage at six consecutive Women’s World Cups.
They had looked set to ease into the last 16 after winning their opening match and then taking a 2-0 lead over Australia last time out, before succumbing to a dramatic 3-2 loss to the Matildas that left them with work to do against Italy.
A draw with the Azzurri would have been enough to guarantee qualification for Vadao’s side, but Marta’s late winner made their progression more comfortable, much to the relief of their passionate fans inside an engaged Stade du Hainaut.
This technical game’s decisive moment came when Italy defender Elena Linari knocked Debinha over in the box, with Marta showing no nerves as she sent the keeper the wrong way from the spot.
Substitute Beatrix had earlier flicked narrowly wide as Brazil had the better of the second half, but their capitulation against Australia has ultimately left them facing a much tougher last-16 tie than they would have hoped for.
The Azzurri, who saw the excellent Cristiana Girelli’s first-half goal correctly ruled out for offside, will play in Montpellier next Tuesday, 25 June.
Their opponents are yet be confirmed, but they will fancy their chances of progressing further, with the Juventus trio of Bonansea, Girelli and Valentina Cernoia again combining well going forward.
Milena Bertolini’s improving side – playing in their first World Cup for 20 years – have caught the eye in this tournament as something of a surprise package.
Ranked 15th in the world – five places below 2007 runners-up Brazil – they started brightly, but came under pressure from the South Americans midway through an entertaining first half.
They looked set to be involved in a goalless World Cup draw for the first time, before Atletico Madrid’s Linari barged over Debinha and Mexican referee Lucila Venegas correctly awarded the spot kick.
But the Italians were still celebrating at full-time with their delighted fans, having secured top spot in a fiercely-contested group that looked wide open before the tournament began.
