Initially an opera singer, he was also an artist whose several albums of paintings include the gallery of stage self-portraits, amounting to a visual autobiography.

He was about to start a military career when his father suggested that he should make a debut as an opera singer which he did in 1834 in Alexandrinka, taking up the leading part in Étienne Méhul's Joseph.

After three years of opera singing he moved to this theatre's drama troupe and enjoyed his breakthrough in 1839, in the leading part of Makar Alekseyevich Gubkin by Fyodor Koni.

Several more creditable performances followed, including Prisypochka (Petersburg Flats, by Fyodor Koni), Almaviva (The Marriage of Figaro by Pierre Beaumarchais), Mitya (The Death of Lyapunov by Stepan Gedeonov), Shvokhnev (The Gamblers by Nikolai Gogol), Chyuzhbinin (Talisman by Grigory Kugushev) The Old Man (Love and Friendship, by Adelaida Taltseva), among others.

For his last ten years on stage Samoylov was the indisputable star of the Imperial Theatre in Saint Petersburg; his benefits included some grand productions like King Lear and Hamlet by William Shakespeare.