Jordan Henderson and Nathaniel Clyne earned their first minutes of the tournament for England, starting alongside club teammates Adam Lallana and Daniel Sturridge - though they were frustrated by Slovakia in a 0-0 draw in their final group game.
James Milner was however benched, as Henderson and Clyne both completed the full 90 and Sturridge and Lallana lasted 76 and 60 minutes respectively. The Three Lions could not muster enough to break down a resilient Slovakian side containing defender Martin Skrtel.
The out-of-favour centre-back looks set to confirm his departure from Merseyside in the coming weeks but turned in a solid performance as captain to protect a valuable clean sheet and a point.
That result in Saint-Etienne allowed Joe Allen's Wales to top Group B after they thrashed Russia 3-0 in Toulouse thanks to goals from Aaron Ramsey, Neil Taylor and Gareth Bale. The midfielder, whose future at the club remains uncertain, set up Ramsey's opener with an excellent through ball.
Delight for all 12 of Reds' internationals as they make it through to first knockout round
But, having played on Monday, both sides had to wait three days to learn who their opponents in the first knockout round would be - England being matched with Iceland after their stoppage-time winner against Austria lifted them to second in Group F.
Meanwhile, the results of Group E - Belgium beating Sweden 1-0 and Republic of Ireland edging a 1-0 win over Italy - pitted Wales against Northern Ireland in a mouthwatering clash, the two teams reaching the knockouts in their first ever Euros thanks to the changed 24-team format.
Radja Nainggolan's 81st-minute strike from range gave Belgium a second consecutive victory - the first time they have registered back-to-back wins at the Euros - with Christian Benteke and Divock Origi both coming off the bench in the dying stages to see out victory.
Benteke had a half-decent opportunity to score after being found in space inside the area, only to put his shot straight at the goalkeeper deep into stoppage-time.
Goalkeeper Simon Mignolet remained on the bench as Thibaut Courtois remained as Marc Wilmots' first-choice, Belgium's win setting them up against Group F winners Hungary in the next round.
Emre Can is also yet to make his first appearance at the competition. He was an unused substitution for the third consecutive game as reigning world champions Germany beat Northern Ireland 1-0 on Tuesday, with later results ensuring a tie against Skrtel's Slovakia - who finished third in England and Wales' group - next up.
There are no Euro 2016 games on Thursday and Friday, with Allen and Wales the first of the Reds' representatives at the tournament to feature on Saturday afternoon.
Can's Germany and Slovakia and Skrtel go head-to-head on Sunday, before the Belgian contingent face Hungary and the next day, the England quartet face Iceland looking to set up a clash with one of Republic of Ireland or hosts France.