The Italo-Brazilian's first international goal saw the Azzurri take control of Group C.
The Inter midfielder struck in the 73rd minute after a neat exchange with Federico Balzaretti to decide a contest which the Azzurri had largely bossed while seeing their hosts make a couple of gilt-edged chances.
Both sides had their moments early on, as Slovenia won a couple of early corners while the Azzurri moved the ball about well. Marco Suler was forced into an excellent cover tackle as Stefano Mauri looked to get in behind the back line with the home side occasionally looking stretched as they chased the ball around.
The four-time world champions came closest in the opening quarter when Alberto Aquilani’s forward run down the right led to Giampaolo Pazzini pouncing on a mistake by Bojan Jokic to strike a first time effort onto the near post. Within moments the home side came as close as they’d been when Robert Koren’s right foot curling effort from 25 yards was superbly pushed wide by the diving Gianluigi Buffon.
Slovenia then had a let-off when Samir Handanovic failed to smother a left wing cross from Riccardo Montolivo, giving Antonio Cassano the chance to get a shot in, but the keeper eventually fell on the ball as the Milan forward attempted to shoot left-footed. Seconds later Christian Maggio covered superbly to get a tackle in on Milivoje Novakovic just as he was lining up a shot.
Just before half-time, Pazzini couldn’t quite get on the end of Cassano’s knock-down, with Bostjan Cesar doing just enough to put him off.
In the early moments of the second half Handanovic pulled off an excellent low save from Stefano Mauri’s shot as Italy continued to build well. At the other end, Buffon was again forced into a save as Zlatan Ljubljankic’s first touch was a right foot drive which the Azzurri skipper had to push away high above his head.
The Azzurri broke through though in the 73rd minute. Thiago Motta collected a ball in midfield and took it back after a touch from Balzaretti before firing low across Handanovic from just inside the box. Over the final 20 minutes or so the Nazionale did what they could to protect what they had without conceding chances, and looked comfortable enough as they held on to a result which sees them stretch their lead at the top of Group C to a dominant six points.
Their next fixture is at home to Estonia in June, with a win potentially booking their place in Poland and Ukraine with two games to play. Slovenia travel to Belfast to face Northern Ireland on Tuesday needing a full three points to get their campaign back on track.