With Ruben Dias and Joao Cancelo also featuring, over 120 gruelling minutes Portugal largely dominated affairs, carving out numerous opportunities but found Slovenia the most obdurate and disciplined of opponents as they fought out a tense, nerve-shredding stalemate.
On a night of the utmost drama at the Frankfurt Arena, Portugal skipper Cristiano Ronaldo also saw a 114th minute penalty saved by Slovenian skipper Jan Oblak.
That led to the drama of penalties – the first at EURO 2024 – and Portugal keeper Diogo Costa saved all three of Slovenia’s efforts with Bernardo converting the crucial third to clinch victory after Ronaldo had atoned from the spot with Bruno Fernandes also on the mark.
All that came after a night high on tension and incident with Slovenia pushing Roberto Martinez’s men all the way.
Dias it was with the Portuguese side’s first chance, the City defender lashing a close range effort narrowly wide with his trusty left foot.
Former Real Madrid superstar Ronaldo was then inches away from breaking his EURO 2024 goal-scoring duck with a 33rd minute free kick that whistled inches over Jan Oblak’s Slovenian goal.
As England found in their group clash with Slovenia, the central European side proved supremely well drilled, fiendishly tough to break down and a real threat on the break.
It was Portugal who dominated possession, territory and chances though with Joao Paulinha seeing his sweetly struck first half injury time strike shave the post.
Portugal picked up where they left off straight after the restart, with Cancelo pushed further forward and proving their most potent attacking outlet.
Brilliant work by Cancelo on 47 minutes set up an inviting opportunity for Bernardo Silva only for the City man to miscue his 15 yard effort.
Oblak then stood tall to deny Ronaldo from another sweetly struck 56th minute set-piece.
But it wasn’t all one way traffic and Slovenia spurned a superb opportunity just past the hour when Benjamin Sesko beat veteran Pepe for pace to be clean in on goal only to fire wide from 15 yards.
Oblak was then there again close on 90 minutes to deny Ronaldo’s angled shot with the match heading into extra time.
Dias had to be alert to deflect a 96th minute Benjamin Verbic shot wide as Slovenia sought to up the ante.
But Portugal then had a golden opportunity to finally break the deadlock on 114 minutes when substitute Diogo Jota was brought down as he powered into the box with referee Daniele Orsato awarded a penalty.
However, Oblak was equal to the challenge, dramatically diving to his left to keep out Ronaldo’s spot kick leaving the Portuguese skipper in tears at the midway break.
The tension continued with Portuguese keeper Diogo Costa then coming to his side’s rescue with a crucial 124th minute block to deny Sesko after Pepe had slipped to leave the Slovenian on his own.
That set up the drama of a penalty shoot-out – the first at the German showpiece – and Josip Ilicic saw Slovenia’s first penalty saved by Costa before Ronaldo then atoned for his earlier miss by this time converting.
Costa then saved Balkovec’s second Slovenian effort with Bruno Fernandes extending Portugal’s lead.
Costa made it a hat-trick of saves by then denying Verbic and Bernardo stepped up to coolly convert and so fire Portugal through with a 3-0 shoot-out win.
Martinez’s side will now train their thoughts on a mouthwatering match-up against France in Hamburg on Friday, July 5.
Kick-off is scheduled for 20.00pm (BST).