Although Perov's parents married soon after his birth, there was no legal way to inherit his father's name and baron title, so he was registered under his godfather's surname — Vasiliev.

He later changed his surname to Perov — a nickname given to him by his teacher who taught him calligraphy as a child (the word pero means feather in Russian).

In 1862, after receiving the right to a state-paid trip abroad together with a golden medal, Perov traveled to Western Europe, visiting several German cities, and then Paris.

Returning to Moscow early, from 1865 to 1871 Perov created his best known pieces, The Queue at The Fountain, A Meal in the Monastery, Last Journey, Troika, the Lent Monday, Arrival of a New Governess in a Merchant House, the Drawing Teacher, A Scene at the Railroad, the Last Tavern at Town Gate, the Birdcatcher, the Fisherman, and the Hunters at Rest.

It was around this period that Perov joined the Peredvizhniki, a collective of Russian realist painters formed as an artists cooperative in protest of academic restrictions.