The formation of a collection of foreign publications on the subject of Russia was historically connected with the war against Napoleon. As early as 1813 the director Alexei Olenin wrote: "The present time, so abundant in glorious events for Russia, demands of the administration of this library that especial care be paid to collecting the fullest possible amount of information on the current war between Russia and France." The first purchases and other acquisitions made (in some cases through the censorship authorities) in 1813-15 represented the start of the purposeful assembly of a collection of Rossica. That was the name given to foreign works about Russia and subsequently to the separate department to which they were allocated in 1850 on the initiative of then-director Modest Korff (prior to this such works had been kept in the History section).

The formation of the collection of foreign works about Russia was a colossal research project of national significance. The project engaged many participants, including renowned historians (S.Soloviev, N.Ustrialov and others), booksellers and antiquarians in St. Petersburg and European capitals, foreign scientists, great collectors and bibliophiles. The Imperial Public Library worked on the project in close collaboration with foreign partner institutions: universities and libraries. The Library's staff were sent, on several occasions, to European countries with an official commission to seek out documents relating to the history and culture of Russia. Rossica's curators selected material about Russia published elsewhere. All such material was recorded in card catalogues immediately after it was acquired by exchange, purchase, or gift.

The collection began to grow rapidly. In 1852 it was enriched by items from the private royal library, founded by Catherine II, which was also known as the Hermitage collection. General Staff Library's vast holdings was transferred to the Imperial Public Library some years later. In 1853 the great collection of rare printed publications relating to Russia was purchased from the bookseller Briff. The senate interpreter Sennitskiy presented over one thousand rare books to the nation in 1860. At the same time, Rossica was supplemented by the rich pamphlet collection on Russian subjects, dating the early nineteenth-century, which was assembled by the Chief Librarian of the Royal Library of Sweden, Klemming.

These passed into the foundation collection of the Imperial Public Library. By the the beginning of 1854, Rossica held more than 10 thousand items. The holdings were increased threefold in the next ten years. The two-volume printed alphabetical catalogue of the department, published in 1873, included over 28,000 titles of books and periodicals and contained 1624 pages. Soon after the appearance of the catalogue, the First International Bibliographical Congress described it as: "the invaluable and unique work". Forty years later, already with 230,000 items, Rossica formed one of the two largest foreign-language collections within the Public Library (the other was the Theological Department).

Of great value is the unique collection of publications of the sixteenth and seventeenth centuries relating to the history of the Russian state. The collection contains such rarities as the first edition of Giles Fletcher's Of the Russe Common Wealth (London, 1591) and a description of Carlyle's Embassy in Russia, published in Amsterdam in 1669.

The collection contains all the first and subsequent editions of these books, as well as their translations into other languages. Among them are 14 editions of the Notes on Moscow Affairs by S. Herbershtein, 19 editions of the Description of a Journey to the Orient by A. Olearius, 14 editions of the Journey of the Northern Countries by La Martinière, and others.

Over a thousand documents are dealing with the French invasion of Russia of 1812, including a copy of Napoleon’s order to invade Russia.

The literary works of various genres reflecting the Russian way of life are extensively represented. Many publications provide responses to the 1905–1907 revolution.

Several thousand books and pamphlets kept are connected with the history of the Russian Empire in the 18th century, including the struggle of Peter the Great against his opponents, palace coups, the history of peasant wars under the leadership of S. Razin and E. Pugachev and other historical events.

The largest number of materials in the collection relates to the history of Russia in the 19th - early 20th centuries. A large number of publications in foreign languages ​​came out in connection with the development of the democratic and revolutionary movement in Russia. Rossica also keeps a huge number of publications reflecting the development of industry, agriculture, transport, trade and finance of the Russian Empire of this period.

In addition, the collection includes many publications on the history of law, religion, archeology, ethnography, geography of Russia, genealogy, heraldry, art history, linguistics. Translations of Russian, Ukrainian, Belarusian, Georgian, Armenian, Azerbaijani writers into foreign languages are fully represented. The collection also includes newspapers and magazines published in foreign languages in Russia, Poland, and the Baltic states.

The elimination of departments and the formation of a single foreign-language section in 1930 meant an end to new acquisitions in the Rossica category. It was reduced to being a self-contained historical collection without, however, possessing the most important features of such collections — beingkept together, having coordinated call numbers and so on. Ideas for the further development of the collection concentrated for the most part on the bibliographical and bibliological assimilation of its colossal store of information. Notably in this context, back in the 1960s A.L.Goldberg and I.G.Yakovleva embarked on a programme still continuing today to publish material on the history of Russia from the library' s foreign-language catalogues.

Items acquired by the Library before 1930 are listed in the Rossica electronic catalogue.