The stock of rare and valuable books of the library is unique. It belongs to the national cultural acquisition of Ukraine.
The library with a 7 000 000-unit collection keeps more than 50 000 early printed books and rare editions, 1800 manuscripts and archival documents, almost the whole repertoire of pre-revolutionary newspapers and journals of Slobids'ka Ukraina, periodicals of civil war period and when Kharkiv was the capital of the Soviet Ukraine. The book's collection of local lore, history and economy was created in the library.
The library preserves collections of incunabula, paleotypes, the books of Cyrillic print of XVI-XVIII centuries, foreign editions of the 2nd part of XVI-XVIII cent., illegal and forbidden by censorship literary works of XIX-XX cent. etc. The uniq ue collection of the books of Cyrrilic and Latin print printed in Ukraine in XVI-XVIII cent. (about 1.000 items) has great value. This collection has 42 monuments of printing (they were preserved in singular copy). The library is proud of the collection of 9 books of 4 editions (1569-1581) printed by Ivan Fedorov.
The collection comprises the books and manuscripts from monastic collections of XV-XVIII cent. from Kyivo-Pechers'ka Lavra, Troitse-Sergyiva Lavra, Dermans'ky monastery in Volyn, Kharkiv Pokrovsky monastery, from school libraries of XVIII-XIX cent. (Kharkiv Collegium, Kamyanets-Podol'ski seminary etc.), the fragments of Romanovs Imperial family's library, from the famous culture workers' libraries such as Melethius Smotrytsky, S. Yavorsky, M. Hnedich, G.P. Danilevsky etc.
There are the monuments of Old Russian and Old Ukrainian written language, archival documents of XV-XX cent. in the collection of manuscript books and archival materials.
The collection of the parchment "Church Service Minea on December' which comprises the oldest copy "the Metropolitan Peter's life" edited by Cyprian (1390), Dionssus Areopagstius, the list of manuscript copies, written documents of XIV-XVI cent., richly illuminated Evangelium of XV-XVIII cent. belongs to the world values of culture. The documents created by the figures of the Ostrog Academy (XVII cent.), manuscript historical collection - "Chronograph" (1610) that contains so-called "Kharkiv" wording of the "Ostrog Chronicler", "The Chronicler" by Petrashka Danovich (1680), "The Chronicler of Samovidets" (XVIII cent.), "The History of Rouses" are of great scientific value.
Among archival documents are Ucases and Circulars with autographs by Empresses Anna Ioanivna and Katherine II as well as autographs by the writers and scientists and personal archival collection of their letters and manuscripts.
All the documents are unique. They have their own distinctive features and were never copied.