Denzel Dumfries headed a dramatic late winner to earn the Netherlands victory after Ukraine had come back from 2-0 down in a Group C thriller in Amsterdam.
Oranje boss Frank de Boer is hoping to use Euro 2020 to prove to fans he is the right man to lead the team into a successful new era after an unconvincing start in the role.
It looked like going to plan for De Boer when Georginio Wijnaldum, who scored eight times in qualifying, pounced from inside the box before Wout Weghorstâ€™s instinctive finish doubled the lead.
But Ukraine pulled one back through Andriy Yarmolenkoâ€™s outstanding 25-yard dipping finish and, four minutes later, Roman Yaremchuk header the equaliser to silence the Dutch fans.
However, Dumfriesâ€™ excellent 85th minute header, after substitute Nathan Akeâ€™s cross, earned the Netherlands victory on their return to the major tournament stage after a seven-year absence.
Fans displayed a flag urging Denmark’s Christian Eriksen, who started his professional career at Ajax, to stay strong after he collapsed the previous day
Dutch fans held up a banner urging former Ajax player Christian Eriksen to stay strong after he collapsed playing for Denmark on Saturday
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De Boer headed into Euro 2020 on the back of 11 games in charge that have seen five wins, four draws and losses to Mexico and Turkey. Not all fans are convinced he is the right man for the role.
Yet his team of youth and inexperience showed grit and determination to edge the highest scoring game of the tournament so far â€“ much to the delight of most of the 16,000 fans in the ground.
While 19-year-old defender Jurrien Timber made just his third appearance for his country, Maarten Stekelenburg started in goal at the age of 38.
It was Stekelenburgâ€™s opposite number, Georgi Bushchan, who looked like frustrating the hosts as he made excellent saves to keep out Memphis Depay and Wijnaldum before the latter opened the scoring, the first of five goals in 33 minutes.
Yarmolenkoâ€™s long-range finish to begin Ukraineâ€™s comeback was the pick of the bunch but it was Dumfriesâ€™ header which lifted the roof as the Netherlands got their campaign off to a winning start.
Georginio Wijnaldum scores for the Netherlands against Ukraine at Euro 2020
Georginio Wijnaldum scored eight goals in Euro 2020 qualifying for the Netherlands
Both teams are back in action on Thursday. While Ukraine take on North Macedonia in Bucharest at 14:00 BST, the Netherlands entertain Austria in Amsterdam at 20:00.