Arkadiusz Milik scored two first-half headers as Napoli came from behind to take the Group B spoils in Ukraine.
Serhiy Rebrov looked set for a dream night as two surprise selections combined for a lovely opener, Denys Garmash lashing in following a cushioned header from 18-year-old Viktor Tsygankov.
Summer signing Milik turned the game on its head before the break, though, with a pair of opportunistic headers over the stranded Olexandr Shovkovskiy.
Dynamo Kyiv gamely sought an equaliser, but a second booking for Serhiy Sydorchuk midway through the second period ended their ambitions.
Key Player: Arkadiusz Milik
No Plan B for Dynamo
That second goal on the stroke of half-time was a killer blow for Dynamo as they really struggled to swing the momentum. Despite putting more emphasis on possession-based football in the second half, they were still dependent on one channel: the right wing and Andriy Yarmolenko. He was the architect of Dynamo’s first goal and in general carried most of the threat for Dynamo; Napoli simply doubled up on him.
UEFA.com team reporters’ view
Bogdan Buga, Dynamo Kyiv (@UEFAcomBogdanB)
A ‘goal in the dressing room’ and a red card for Sydorchuk early in the second half were too much for Dynamo, who battled hard, fought until the end but were unable to salvage anything from the game. A home defeat in the first match – what could be worse for a team not considered favourites in the group? But it’s far from the end. Dynamo showed potential, they showed perspective in 18-year old Tsygankov, and they showed character.