The second matchday in Group B pitted the reigning European Champions against a Spain side looking to replicate the Euros success of 2008 and 2012.
The pattern of the contest was established from the off as Spain launched a relentless onslaught to pepper Italy's goal in the opening 25 minutes.
Pedri, Nico Williams, Alvaro Morata and Fabian Ruiz all threatened to break the deadlock in a dominant first period, but Italy ultimately stood firm to scrape through to half-time unscathed.
La Roja showed no signs of letting up, and their constant pressure ultimately told in the 55th minute when Riccardo Calafiori inadvertently sent the ball into his own net.
A second Spain goal appeared more likely than an Italy equaliser, but Luis de la Fuente's young guns had to settle for just a narrow victory which ensures Spain will participate in the knockout rounds of a fifth consecutive European Championships.
Williams and co pile pressure on Italy
Buoyed from their dominant 3-0 win over Croatia, Spain threatened to take the lead inside the opening two minutes in Gelsenkirchen.
Williams neatly worked the space to stand the ball up for Pedri to attack, but the midfielder was unable to his head over the ball, giving Gianluigi Donnarumma the chance to tip over the bar.
Williams then spurned a glorious opportunity, sending his header wide from Alvaro Morata's inch-perfect delivery from the left flank.
As the contest moved past the 20-minute mark, Morata found himself in more familiar terrority, receiving the ball in the box before taking one touch too many, allowing Donnarumma to close the angle and make a strong near-post stop.
With Spain unable to convert the conventional chances, Ruiz took it upon himself to unleash a thunderous long-range strike which required another important intervention from Donnarumma.
Italy boss Luciano Spalletti would have been disappointed by the fact his troops failed to register a single shot on target in the first period, but the only saving grace was that the contest remained goalless at the break.
Spain get deserved breakthrough
In an attempt to turn the tide, Spalleti turned to his bench at the interval, introducing Roma's Bryan Cristante and Juventus' Andrea Cambiaso.
However, those changes failed to have the desired effect as Spain continued to open up the Italian defence, with Pedri arriving in the box to meet Marc Cucurella's neat pullback, only to guide the ball harmlessly wide of Donnarumma's goal.
With Spain unable to take advantage of their clearcut chances, they were ultimately given a massive helping hand when Calafiori diverted the ball into his own net in the 55th minute.
Williams drove towards the byline before sending a cross which was met Morata, who forced Donnarumma to parry with his left hand, causing the ball to bounce off the unfortunate Calafiori and into the net.
After playing a key role in the opener, Williams nearly put his own name on the scoresheet when he cut inside from the left and unleashed a thunderous strike against Donnarumma's crossbar.
Substitute Ayoze Perez threatened a couple of times in stoppage time, but Spain was unable to grab a deserved second goal.
As for Italy, they finished the contest with just one shot on target and very rarely looked like finding a way back into the contest.
Man of the Match - Nico Williams
Cucurella, Ruiz and Yamal all have claims to be awarded Man of the Match following their contributions in the statement victory.
However, Williams probably just edges out his teammates, especially after he sent in the dangerous cross that led to the decisive goal.
The Athletic Bilbao winger was a constant threat on the left flank and can count himself unlucky that he did not get his name on the scoresheet.
What next for Spain and Italy?
Having secured top spot in Group B, De la Fuente may be tempted to rotate his squad for Monday's clash with Albania.
In contrast to La Roja, Italy still have work to do after suffering their first defeat since losing to England in October 2023.
The Azzurri are currently in second place and two points better off than Albania and their final group-stage opponents Croatia.