Harlamoff was born close to Saratov on the Volga River, and enrolled at the Academy of Fine Arts in Saint Petersburg at the age of 14. He won a gold medal in 1868 for his painting entitled The Return of the Prodigal Son. This enabled him to study in Paris at the École des Beaux Arts under the great portrait painter and teacher Leon Bonnat. Harlamoff’s talent in this area soon became clear as Emile Zola rated his portrait of Ivan Turgenev as amongst the best works of the Paris Salon of 1876. He regularly exhibited at the Paris Salon and won a second-class medal at the 1878 Paris Universal Exhibition.
Harlamoff learned his skills copying old master paintings such as Rembrandt's Anatomy Lessons. He painted many military scene's and covered religious subjects in his early years. When his career evolved he became a respected portrait painter with important sitters as Tsar Alexander II, Prince Demidoff-San Domato and Ivan Tourguéneff. Harlamoff is however best know for his informal portraits of sitters who he painted for their beauty and innocence. Harlamoff often used flowers to symbolise the short-lived innocence of youth. He preserved the Russian ambience in the details of for example a dress or facial features.
Queen Victoria greatly admired his painting of children playing with flowers that was exhibited at the Glasgow International Exhibition of 1888. Harlamoff came to the attention of wealthy American and European collectors who appreciated his idealised portraits of young women and girls.
The question about the time and the place for death of Alexei Harlamoff remains open. In literature it is most frequently indicated he died in Paris in 1922. Claims he died in Saratov are not likely to be true. Books with the records about death in 1922 from the Civil Registry Office Saratov were preserved completely, but his name is not mentioned. In 2005 a painting signed by Harlamoff and dated 1923 was discovered in a private collection.
Harlamoff is represented in the following collections: J. Paul Getty Museum, Los Angeles; The Athenaeum; Chi-Mei Museum, Taiwan; Alexander III Museum, St Petersburg; Tretyakov Gallery, Moscow, amongst others.