The library was founded by Peter I, although the decree itself has not survived and the date of foundation is considered to be September 1714 — the start of the loaning of books from the library to the readers.

It was the first state public library in Russia. Its fund consists of manuscripts and books of the Kremlin Royal Library in Moscow, the personal collection of Peter I in the Summer Palace, the Pharmacy Order, the Gottorp Library of the Dukes of Holstein, the Mitava Library of the Dukes of Courland, as well as book and manuscript collections of Peter I’s associates.

In 1901, due to the dilapidation of the heating system, a fire broke out in the Library, during which more than 1,500 volumes of valuable publications were lost. This event accelerated the decision on the construction of a new building for the Library. In 1910, a government estimate was approved for the construction of a new Library building; in 1914, the construction was completed, but due to the outbreak of the World War I, the building was transferred to the War Ministry, which accommodated the 166th consolidated evacuation hospital here. The library moved into this building only in 1925.

Since 1932, the library network of the Academy of Sciences has included libraries of its provincial bases and branches in the European part of the country, Siberia and the Far East. In 1934, a special branch of the library was created – the Moscow Branch of the Library of the Academy of Sciences (MOBAN). In 1973, on the basis of MOBAN, the Natural Sciences Library was established, which received the status of an independent library of the Academy of Sciences.

Since the early 1930s, the Library has become an academic repository of handwritten and old-printed books. The Laboratory for the Restoration and Preservation of Documents was reassigned to the Library as an independent library unit.

During the Great Patriotic War (1941-1945), the Library of the Academy of Sciences was put on a war footing. Already in July 1941, the most valuable materials of the seven-million fund were prepared for evacuation. The rapid approach of the battle front to Leningrad did not allow them to be sent to the rear: on September 8, 1941, the stronghold tightened around the city. All the books and materials prepared for shipment remained in the Library. They were moved to the semi-basement of the building; its windows were covered with sand, shields and earth.

On May 10-12, 1988, a UNESCO mission visited the Library, consisting of: the Head of UNESCO for Information Programs and Services J.Tokatlian, President of the International Federation of Library Associations and Institutes (IFLA) H.P. Geh, Executive Director of the International Union of Archives K. Ketchkemeti and member of the UNESCO Department for the General Information Program V. Montviloff. Deputy Director General T. Keller, in a letter to Academician I.A. Glebov, highly appreciated the solidarity and determination of the library staff, readers and the authorities in restoring the library affected by the fire.

In 1988, a fire broke out in the library again, and in 1994 the Library completed a documentary check of the funds, compiled lists of losses, lists of books to be written off, lists for replenishing funds and continued servicing readers in the same mode.

In 2014, the Library of the Russian Academy of Sciences celebrated its 300th anniversary.