Neither nation has lifted the Henri Delaunay Trophy aloft since the inception of the continental championships, and both Denmark and Slovenia will provide further stiff competition for the coveted knockout places.
Match preview
Two-time runners-up of the European Championships in 1960 and 1968 during their Yugoslavia days, Serbia are making a debut of sorts at this year's edition, having never before qualified for the quadrennial continental gathering as an independent nation.
Led by head coach Dragan Stojkovic - regarded as one of the finest talents to ever don the Serbia strip - the Eagles recorded a mixed bag of qualifying results with just four wins from their eight contests, but their 14-point total was enough for a runners-up finish behind Hungary.
Serbia's results in the preliminary section did at least follow a consistent pattern - they did the double over Lithuania and Montenegro, drew twice with Bulgaria and suffered a pair of defeats to the Hungarians - thereby ending a 24-year exile from the Euros since Yugoslavia's run to the quarters in 2000.
Brimming with recognisable names in the final third, including Juventus hitman Dusan Vlahovic, Ajax cult hero Dusan Tadic and Al-Hilal pairing Sergej Milinkovic-Savic and Aleksandar Mitrovic, Serbia's recent form has not left much to write home about, only amassing four wins from their last 11 contests.
However, two of those successes have come in their last three friendly battles - edging out Cyprus 1-0 and putting three past Sweden either side of a narrow defeat to Austria - and England's unremarkable June exploits should leave Stojkovic's men optimistic of denting the Three Lions' football's-coming-home aspirations.
Fewer than three full years have passed since the nation exploded into ecstasy as one at Wembley, where Luke Shaw's tidy back-post volley sent England on their way to a long-awaited slice of European glory, before the Italian old guard inflicted more penalty heartbreak on the crestfallen hosts.
Despite renewed criticism of his tactical approach and brief talk of interest from Manchester United - which has now died down - Gareth Southgate continues to bark orders from the England touchline and navigated an unbeaten qualification period in the wake of an all-too familiar quarter-final elimination at the 2022 World Cup.
Two revenge wins over reigning champions Italy were among England's six preliminary successes, but the Three Lions may have had their pre-tournament favourites label ripped off them if recent exploits are anything to go by, as Southgate has masterminded just one win from five.
Even that success - a 3-0 beating of Bosnia-Herzegovina - was a tedious affair until the hour mark, and more Iceland-inflicted misery followed in a 1-0 loss to their Euro 2016 conquerors at Wembley, where 90 minutes of huffing and puffing counted for nought due to a severe lack of killer instinct.
Of course, Southgate chopped and changed his selection over the course of the friendly period, and not since their Euro 2004 opener against France have England - who tackle Serbia for the first time since the breakup of Yugoslavia - been beaten in the group stages, but even that statistic may not comfort the glass-half-empty brigade.
Serbia form (all competitions):
L
D
L
W
L
W
England form (all competitions):
W
D
L
D
W
L
Team News
Unlike some Euro 2024 competitors, Serbia came through the June warm-up period unblemished on the physical front and have all of their big-hitters available, meaning that Stojkovic is facing the best kind of selection dilemma in the final third.
The Eagles boss has tended to avoid starting both Vlahovic and Mitrovic up top and could stick with such an approach here, thereby allowing Tadic - the most-capped Serbia men's player of all time with 108 appearances - to return to the attacking third.
There should also be scope for Nemanja Maksimovic - rested for the Sweden win after a blow to the head against Austria - to return to the engine room, while Werder Bremen's Milos Veljkovic should return to the three-man defensive wall in front of either Predrag Rajkovic or Vanja Milinkovic-Savic.
As for England, Southgate appears to have avoided an illness scare over key defender John Stones - also the victim of an ankle knock in the Iceland loss - who was successfully quarantined to his bedroom and is now training as normal again.
Consequently, Southgate's only absentee for Sunday's opener should be Luke Shaw, who is training fully once more following a muscular problem but will not be risked just yet, meaning that Kieran Trippier will continue to hold the fort on the left.
Fundamental attackers Jude Bellingham and Bukayo Saka are both raring to go after their well-earned rest periods, and Southgate is also expected to give Trent Alexander-Arnold the nod in a midfield position after his exceptional work against Bosnia.
Serbia possible starting lineup:
V. Milinkovic-Savic; Veljkovic, Milenkovic, Pavlovic; Zivkovic, Maksimovic, Lukic, Kostic; S. Milinkovic-Savic, Tadic; Mitrovic
England possible starting lineup:
Pickford; Walker, Stones, Guehi, Trippier; Alexander-Arnold, Rice; Saka, Bellingham, Foden; Kane
We say: Serbia 1-2 England
As a third of Serbia's qualifying goals came from headers - the highest ratio of any of the 24 teams at Euro 2024 - and England are without their aerial dominator in Harry Maguire, expect to see Jordan Pickford's goal breached at least once at the Veltins-Arena.