Tine De Caigny's second-half strike settled a tight contest and took Belgium into the knockout rounds for the first time, setting up a quarter-final with Sweden.
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Belgium fended off a determined Italy at the Manchester City Academy Stadium to reach the UEFA Women's EURO knockout stages for the first time.
49' De Caigny puts Belgium in front
52' Girelli effort crashes off crossbar
79' Giacinti drills narrowly wide
90+1' Wullaert strikes post
Match in brief: Red Flames make history
As the final group stage matches kicked off, the Group D runners-up slot was still in reach for three teams: Italy, Belgium and Iceland – who were playing section winners France in Rotherham.
With less than a minute gone, Cristiana Girelli pounced on a wayward Belgium pass, forcing Nicky Evrard into early action. However, the Red Flames engineered two chances shortly after, Hannah Eurlings firing off target before Elena Dhont's outstretched leg was a fraction away from connecting with Tessa Wullaert's cross from the right.
Manuela Giugliano's solo effort from the edge of the box inside 18 minutes sailed narrowly wide as the Azzurre began to grow into the match. Utilising the flanks as their main attacking outlet, Italy's best chance of the first half came from Barbara Bonansea's cross-shot, as she jagged in from the right channel and fizzed across the face of goal.
An exciting second half ensued when in an unexpected turn, Tine De Caigny launched Belgium into the lead as Italy failed to clear their lines. As Group B stood, Belgium would be going through. Girelli looked to equalise immediately, but her fine effort crashed off the crossbar.
Italy piled on the pressure and in the 79th minute, Valentina Giacinti drilled desperately wide of the post. However, Belgium had now reshaped into a compact 4-1-4-1 system, which was proving tough for the Italians to penetrate.
In extra time, Wullaert broke free to strike the post, before Belgium dug in as the Azzurre gave their all. However, it was Ives Serneels' team's night as they clinched the Group D runners-up spot to qualify from the group stage for the first time and set up a quarter-final with Sweden on Friday 22 July in Wigan & Leigh.
Player of the Match: Sari Kees (Belgium)
"She was strong in defence and marshalled Belgium's back line, making important clearances and executing passes when in possession."
UEFA Technical Observer panel
Vieri Capretta, Italy reporter
It's all over for the Azzurre. Too many players did not live up to expectations and that opening loss against France probably killed the confidence in the squad. They could have won today, but in the end lacked the goalscoring instinct to turn things around. The Azzurre will be going home with many regrets.
Alyssa Saliou, Belgium reporter
Blood, a lot of sweat and some tears, but Belgium march on! A historic evening. It looked like Italy were going to get the equaliser and Iceland were going to walk away with it all, but the Red Flames managed to pull it off. Quarter-finals here we come!
Sari Kees, Belgium defender: "We were fighting until the end but I feel like we deserved this. It's amazing, really. Italy are such a strong team but we just didn't give up. We kept on going. In the end, that's what made the difference."
Ives Serneels, Belgium coach: "This is a historic night for Belgian women's football. I've had a lot of good moments in my career but this is definitely up there. This might be the best moment yet. It has been a long time in the making: I've been with the Belgian women's national team for 11 years now. So I'm ecstatic that we're going to the quarter-finals!"
Milena Bertolini, Italy coach: "The girls played well; they gave everything they had. This tournament has been an important experience and it will help us grow for the future. We'll analyse our mistakes and take with us the good things we did, in order to improve."
Barbara Bonansea, Italy striker: "Yes, we lost but we learnt that nothing can be taken for granted. Every moment should be cherished, so I'll look back at this tournament with a smile."
- Belgium have qualified from the group stage for the first time – on their second appearance.
- Italy have won only one of their last eight EURO tournament matches (D1 L6).
- Belgium have scored in their last five EURO finals fixtures.
Italy: Giuliani; Di Guglielmo (Bonfantini 46), Bartoli, Linari, Boattin; Bergamaschi (Cernoia 80), Simonetti (Giacinti 68), Rosucci (Caruso 58), Giugliano; Bonansea, Girelli (Sabatino 80)
Belgium: Evrard; Vangheluwe (Deloose 66), Kees, Biesmans, Philtjens; Cayman (Missipo 90+2), Vanhaevermaet, De Caigny; Dhont (Minnaert 59), Eurlings (Delacauw 66), Wullaert
Belgium will face Sweden in the quarter-finals on Friday 22 July at Leigh Sports Village.