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Marc Wilmot’s Belgium, the highest ranked side coming into the European championship finals, dominated for long spells of the Group E clash at the Stade de Lyon.
But Giaccherini’s strike just after the half hour and Southampton striker Pelle’s stunning finish in stoppage time meant it was future Chelsea manager Antonio Conte’s men who took the three points as they look to emulate their run to the Euro 2012 final.
Sweden’s 1-1 draw with the Republic of Ireland earlier at the Stade de France means Italy go top of the group.
Torrential rain in Lyon before kick-off meant both sides had to cope with a greasy ball.
But Belgium dominated the opening exchanges on their first appearance at a European finals since co-hosting Euro 2000.
The Red Devils enjoyed the lion’s share of possession in the initial stages and tested Italy’s veteran skipper Gianluigi Buffon, appearing at his 11th major finals, in the Azzurri goal.
A well-worked move involving Romelu Lukaku and Marouane Fellaini allowed Radja Nainggolan a long-range strike on 10 minutes which forced Buffon into a diving save.
Yet, Italy’s ‘BBC’ defence, Andre Barzagli, Leonardo Bonucci and Giorgio Chiellini, stood firm to deny the Belgian attack and the Italians then took the game by the scruff of the neck midway through the first-half which yielded Giaccherini’s opener.
Approaching the half-hour mark, Pelle had Italy’s first clear chance when his strike from outside the area flew wide of Thibaut Courtois’s far post.
On 32 minutes, Bonucci’s long floated pass found Giaccherini in behind the Belgium defence to stroke his shot past Courtois.
The opening goal spurred on the Italian attack and Candreva’s shot forced a save before Pelle headed wide as the Italians finished the stronger of the first-half.
The Belgians were first to threaten after the break and Lukaku had his head in his hands as his shot clipped the post on 52 minutes before Hazard’s crisp shot tested Buffon.
Then centre-back Toby Alderweireld, Vincent Kompany’s replacement in the Belgium defence after a groin injury ruled him out of Euro 2016, had to scramble back to deny Eder.
Belgium’s captain Hazard moved from the left wing to the middle of the attack for the second-half, but the Chelsea star was frustrated in his efforts to free up Lukaku.
The Everton striker made way for Liverpool’s Divock Origi, whose header from a Kevin de Bruyne cross flew just over, as Marc Wilmot’s Red Devils pushed for the equaliser.
With time running out, Courtois pulled off a fine save to deny Italian substitute Ciro Immobile.
However, there was nothing the Chelsea ‘keeper could do as Italy sealed the three points in stunning fashion deep into stoppage time when Pelle smashed home Antonio Candreva’s cross.
Conte’s Italy next face Sweden in Toulouse on Friday, whilst Belgium face a crucial clash with Ireland on Saturday in Bordeaux if they are to avoid an embarrassing early exit.