Italy, who had only named two starters from the XI that began their Matchday 2 match against Hungary, created the first chance three minutes in. The home backline was dissected by Lorenzo Pellegrini's clever pass, but Davide Frattesi side-footed agonisingly wide.
Austria had shown their ability to punish generosity in their 3-0 win over Croatia, and Andreas Weimann pounced when given space in front of goal, slotting in Konrad Laimer's incisive 37th-minute cross after Marko Arnautovic's deception.
Jonas Hofmann's second-half strike looked like it would condemn England to a second successive loss in the tournament, but Kane made sure that would not be the case, picking himself up to score his 50th goal for the country after being brought down in the box five minutes from time.
Both Croatia and France were coming off defeats in their previous matches, which made for a tense start to the game. However, with France coach Didier Deschamps making ten changes following his team's loss to Denmark, it was no surprise that the hosts created the first real chance.
Spain went into the game at La Cartuja Stadium in Seville knowing they needed a win to finish ahead of Germany in their group.
The Italians doubled their lead eight minutes later when Ciro Immobile slid a through ball to Kean, who beat keeper Lukas Hradecky to become the first player born this century to score for Italy.
The Spanish national team faces an important UEFA Nations League tie away in Croatia on Thursday as they look to assure that they finish on top of their qualifying group.
The 25-year-old looks to be in his element, more often than not, when playing for his country.
Poland also had a couple of chances in the second half with Kamil Grosicki denied by Gianluigi Donnarumma, with Arkadiusz Milik curling over.
Belgium's second win of the fledgling tournament keeps them flying high in League A Group 2 following an opening 3-0 win in Iceland.
