The first competitive meeting between the two nations sees a resurgent Romanian side arrive in Germany as qualifying group winners, while their opening opponents edged through via the playoffs.
Match preview
Taking part in a sixth European Championship - and first since 2016, when they finished bottom of their group with just one point - Romania are intent on progressing to the knockout phase this summer.
Historically, the Tricolorii's win rate of 6% at Euro finals suggests that may prove a tough task - their sole success in 16 games was beating England at Euro 2000 - but results over the past year have raised expectations.
Capping off a superb campaign, Romania beat Switzerland in their final qualifier to top Group I unbeaten, winning six and drawing four of 10 fixtures en route to Germany.
After conceding just five goals in the process, their defensive capabilities have been confirmed in recent friendlies: a 3-2 defeat to Colombia aside, the Tricolorii leaked only one goal in draws against Northern Ireland, Bulgaria and Liechtenstein.
Of course, being pitched into a Euro 2024 group containing Belgium, Slovakia and Ukraine puts them up against far more challenging opponents, but Edward Iordanescu's men may still feel that they can progress - particularly as several third-placed teams will go through.
Since taking charge in 2022, Iordanescu has improved his nation's standing significantly, and the 45-year-old now leads Romania into a major tournament. In fact, he is the first man to do so since his father Anghel Iordanescu - also mastermind of the fabled World Cup '94 campaign - did so at Euro 2016.
Though, like Romania, they missed out on Qatar 2022, Ukraine are now making a fourth consecutive appearance at UEFA's continental championship, in which they have rarely fared well.
Losing eight of their 11 matches to date, the Ukrainians have failed to even score in six of nine group games - but they did make it through to the quarter-finals three years ago.
This time, the war-torn nation are aiming to produce a similar result in order to raise morale back home, after almost missing out on a place at the finals altogther.
Finishing third in qualification behind England and Italy left them relying on a playoff spot earned by their previous UEFA Nations League performance, and Serhiy Rebrov's side then squeezed past Bosnia-Herzegovina and Iceland thanks to two late winners.
Rebrov is managing at his first major tournament, and as the former Tottenham Hotspur striker did not appear at a European Championship during his illustrious playing days, he will now have a first taste of the Euros.
Results in the build-up have been mixed, as a goalless draw away to Germany was followed by a 3-1 defeat to Euro 2012 co-hosts Poland, with Ukraine conceding three times inside the opening half-hour; nonetheless, a subsequent 4-0 thumping of Moldova lifted spirits ahead of Monday's opener.
Romania form (all competitions):
W
W
D
L
D
D
Ukraine form (all competitions):
D
W
W
D
L
W
Team News
Due to a lack of goals in 2024, some debate remains as to the identity of Romania's lone striker for the Euros, with Denis Alibec, George Puscas and Denis Dragus all vying to start up front.
In goal, veteran stopper Florin Nita is hoping to supplant Atletico Madrid's Horatiu Moldovan, who has not featured for the Spanish side since joining in the winter transfer window.
Captain Nicolae Stanciu is a certain starter in midfield, having scored 14 goals in his international career to date, but skilful winger Olimpiu Morutan has been ruled out of this summer's action due to an ACL injury, leaving the door open for Parma duo Valentin Mihaila and Dennis Man.
Meanwhile, Serhiy Rebrov's first-choice left-back will be unavailable on Monday, as Vitaliy Mykolenko has sustained an ankle injury, so Oleksandr Zinchenko is expected to switch from midfield to cover the Everton defender's absence.
Mykhailo Mudryk and Viktor Tsygankov are set to feature out wide, and Shakhtar Donetsk star Heorhiy Sudakov should take an advanced role in midfield.
With two goals and three assists, Andriy Yarmolenko has been involved in five of Ukraine's eight goals at European Championships, but Artem Dovbyk claimed La Liga's Pichichi award in a successful first season for Girona and will most likely start up front.
Romania possible starting lineup:
Nita; Ratiu, Dragusin, Burca, Bancu; M. Marin, R. Marin; Man, Stanciu, Mihaila; Dragus
Ukraine possible starting lineup:
Lunin; Konoplya, Zabarnyi, Matviyenko, Zinchenko; Shaparenko, Stepanenko, Sudakov; Tsygankov, Dovbyk, Mudryk
We say: Romania 0-1 Ukraine
As Ukraine clearly pack more punch up front, a tight contest should swing their way and result in three precious points.