The 27-year-old completed his move to the Bundesliga club on Monday, putting pen to paper on a four-year contract.
His arrival comes on the same day Ousmane Dembele finalised his switch from Dortmund to Barcelona in a massive transfer worth an initial €105m.
Yarmolenko's move ends a 10-and-a-half-year stay with Dynamo, where he won Ukraine's Premier League on three occasions.
"Andriy is a player we have been pursuing for a long time and who is on top level both at club level and in the service of the Ukrainian national team for football," Dortmund sporting director Michael Zorc told the club's website.
Yarmolenko himself added: "I am very grateful that Dynamo Kiev has fulfilled my dream of being able to switch to a big European club!
"I will work hard in every training to help BVB achieve its highest goals - that's what I always do."