In 1899 Golovin participated in exhibitions of the group Mir Iskusstva (“World of Art”); since 1902 he was a member of this society. In 1903 he joined the Union of Russian Artists. In 1898 he was appointed the scene painter of the Imperial Theatres. He also designed the performances of the Bolshoi Theatre, in particular the opera by A. N. Koreshchenko Ledyanoy dom (“Ice House”, 1900) and the opera by N. A. Rimsky-Korsakov Pskovityanka (“The Maid of Pskov”, 1901). In 1901 Golovin moved to St. Petersburg; since 1902 he served as a chief scene painter of the Imperial Theatres and the consultant of the directorate on art issues. He worked for the Aleksandrinsky and the Mariinsky Theatres, and created costume and scene designs to the operas Carmen by Georges Bizet (1908), Orpheus and Euridice by K. V. Gluck (1911), The Stone Guest by A. S. Dargomyzhsky (1917); plays At the gates of the kingdom by K. Hamsun (1908), Thunderstorm by Alexander Ostrovsky (1916), Masquerade  by M. Lermontov (1917), Song of the nightingale by I. F. Stravinsky (1919) and many others.

Since 1902 Golovin together with the director of the Imperial Theatres V. A. Telyakovsky visited Paris, Italy, Holland, Austria and Belgium. In 1905 Golovin’s works were exposed at the Tauride Palace in St. Petersburg. In 1906–1907 he participated in the exhibitions of the Russian art, organized by S. P. Dyagilev in Paris and Berlin.

In 1908–1917 Golovin cooperated with V. Meyerhold. In 1909–1910 he designed the productions of Dyagilev entreprise (Russian Seasons) in Paris. He created scene and costume designs together with N. V. Roerich and D. S. Stelletsky for the operas Boris Godunov by M. P. Mussorgsky, The Maid of Pskov by N. A. Rimsky-Korsakov, and for the ballet Zhar ptitsa (“Firebird”) by I. F. Stravinsky.

In late 1900s — early 1910s Golovin worked in the art and ceramic workshops under P. K. Vaulin in Kikerino near St. Petersburg.

In 1912 Golovin was elected a member of the Imperial Academy of Arts (IAKh). In 1913 he settled in Detskoye Selo near St. Petersburg.

After the revolution, Golovin actively participated in the work of the House of Arts. In 1919 he exposed his works at the First State Free Exhibition of works of art, exhibitions of the theatrical decorative art in Leningrad (1927) and in Moscow (1928). In 1926 Golovin cooperated with K. S. Stanislavski at Moscow Art Theatre, where he designed the productions Crazy Day or the Marriage of Figaro by Beaumarchais (1927), Othello by W. Shakespeare (1930). In 1928 he was conferred the title of the People’s Artist of the RSFSR (Russian Soviet Federative Socialist Republic).

Retrospective exhibitions of Golovin’s works were held in 1940 in the State Russian Museum in Leningrad, in 1956 — in the exhibition halls of the USSR Academy of Fine Arts in Moscow and in Leningrad, in 1983 and 1988 — in the A. Bakhrushin State Central Theatre Museum in Moscow.

Alexander Golovin was one of the most significant artists of the 19th — the 20th century. The peak of his work was in 1900s–1910s; at that time Golovin was close to modernism. The artist managed to develop his own recognizable style. Unusual, sometimes even excessive, brilliance, courtliness of graphic ideas and solutions were characteristic for his works. Golovin’s favorite motifs were ornamental elements in his ceramic works, in his sketches, pictorial panels, and scene designs.

Works by Alexander Golovin were in many museum collections, including the State Tretyakov Gallery, the State Russian Museum, the Pushkin State Museum of Fine Arts, the A. Bakhrushin State Central Theatre Museum and many others.