The Museum's library contains rare and valuable hand-written and printed books from 1500 to the end of the 19th century. The collection contains Greek and foreign-language books, through which the visitor can observe the literary evolvement of Greece's Enlightenment. It consists of editions from Greek printing shops in Venice, Vienna, Paris, Constantinople, Moscow, Leipzig, Pest, Florence, London, Amsterdam, Malta, Trieste, etc.

The Museum owns unique collections and series of books that were published in different European cities during the 16th – 20th century, by Greek intellectuals who resided in these cities, as well as rare first editions that were printed after Greece's liberation.

They are unique samples of the intellectual movement, the educational level and the interests of Greek intelligentsia during that period.

They are early editions of ancient Greek and Latin authors and French classics from the 16th-18th century, a large number of which were printed with the aim of educating Greeks in order to prepare them intellectually for the great revolution of 1821.

The collection also contains the first Greek editions after the liberation and series of educational, encyclopedic, scientific, philological and other books, to the end of the 19th century.

Another interesting category are the books, magazines and newspapers that cover the period from the end of the 19th century to the 1940s.

There is also a separate collection of books relating to Skyros, containing books that were written by Skyrian and foreign authors. Among others, there are manuscripts, articles and complete works by Skyrian and other intellectuals, such as Konstantinos Faltaits, Ageliki Hajimichali, Agathocles and Michael Konstantinides, Efrosini and Christopher Samartzidis, etc.