The library was founded in 1813 as the "Duchy of Nassau Public Library" by the Nassau government. In 1814, the library was granted the right to hold compulsory copies for Nassau. The collection was based on the Princely Reference Library in Biebrich Palace and the Government Library of Nassau-Usingen (founded in 1730). Until 1822, parts of the Nassau monastery libraries (Eberbach, Hadamar, Rommersdorf, Sayn, Schönau, Marienstatt), which had been dissolved during secularization, were added to the library, as well as a large part of the library of the (Reformed) High School in Herborn. A certain focus of the collection in the 19th century was balneology.

With the annexation of Nassau by Prussia in 1866, the library became the "Royal Library of Wiesbaden". On April 1, 1900, it was transferred to the administration of the city of Wiesbaden and now operated under the name "Nassau State Library". The name "Städtische Bibliothek", which was proposed several times at the time, did not succeed and was only used temporarily during the First World War. In 1938, the library was taken over by the Bezirksverband für den Regierungsbezirk Wiesbaden (Bezirkskommunalverband Wiesbaden); with its integration into this administrative structure, which was strongly influenced by National Socialism, the library temporarily lost its academic freedom and thus its status as an intellectual center of attraction in the city and region. In 1953, the new federal state of Hesse took over the sponsorship.

In 1942 and 1943, the most precious manuscripts, including the Rupertsberg "Scivias" Codex of Hildegard of Bingen (12th century), were moved to Dresden, where they were lost at the turn of 1945/46. Apart from this sensitive loss, the library survived the war largely unscathed and experienced a new heyday during the long period under the direction of Franz Götting.

Known as the "Hessische Landesbibliothek" from 1963 to 2011, the library was integrated into the RheinMain University of Applied Sciences in 2011 and now forms the "RheinMain University and State Library" together with the former University of Applied Sciences Library. It continues to function as a universal academic library with a focus on regional literature, but also provides students with basic literature.

The so-called Nassovica collection (approx. 55,000 titles, including a considerable amount of Wiesbaden literature) with its often very rare monographs, journals, newspapers and maps from five centuries forms the heart of the library and is constantly being expanded - now also through electronic media. The library currently holds a total of around 815,000 volumes, including 442 manuscripts and 445 incunabula, of which the "giant codex" of Hildegard von Bingen is particularly noteworthy. In 2004, the "Hessische Fachstelle für Öffentliche Bibliotheken" (until then: "Staatliche Büchereistelle") was integrated as a department. The library was initially housed in the Old Palace before moving to the Erbprinzenpalais in Wilhelmstraße in 1821. It has been located in Rheinstraße since 1913.