His father was Russian diplomat Ivan Matveyevich Tolstoy. His brother was Dmitry Ivanovich Tolstoy (1860–1941), who was director of the Hermitage in Saint Petersburg.

He served as Vice President of the Russian Imperial Academy of Arts while Grand Duke Vladimir Alexandrovich was Academy President. He later served as Imperial Minister of Education in the Witte Government.

• Out of My Past: The Memoirs of Count Kokovtsov Edited by H.H. Fisher and translated by Laura Matveev; Stanford University Press, 1935.
• The Memoirs of Count Witte Edited and translated by Sydney Harcave; Sharpe Press, 1990.

• Works by Ivan Ivanovich Tolstoy at LibriVox (public domain audiobooks)