The National Library of Serbia was founded in 1832, and it is the oldest cultural institution in Serbia. It was created as a special depository of books, then as a library within the Ministry of Education, and since then the library gathered many libraries, public and state authorities and bought out several private libraries, which have grown over time into the National Library.

By the order of the Prince in 1853, the profession of State Librarian was introduced, in the rank of a high school professor. The name of the “National Library” was established by Djura Daničić, who defined the national conception of the purchasing policy and began compiling the current national bibliography.

The First World War brought a lot of misfortune to the Library. The bombing destroyed a part of its holdings, and the remaining collections were moved for safety to several different places in Belgrade, Niš and Kosovska Mitrovica. A part of the collections ended up in Sofia, but was returned after the war. A lot of the library materials, manuscripts, books and newspapers disappeared. 

During the Second World War, on April 6th 1941, during the bombing of Belgrade, the complete library was burnt to the ground. A great part of the holdings, catalogues and inventory, were destroyed at that time. The reconstruction of the library holdings began during the war, and was intensified after the war.

By the Serbian Libraries Act from 1965, the National Library, as the central parent library in Serbia, was given a special position and many important functions. 

On the anniversary of the bombing destruction, April 6th 1973, the Library solemnly opened the doors of its new building, where it is still situated today. 

In 1996, the Library obtained its local computer library network, when the access to Internet was facilitated and the first web site presentation of the National Library of Serbia was made.

Since 2000, the Library has made important steps, in the first place regarding its opening towards the world, whereby the Center for International Cooperation received a more intensive and important role. The Center for Scientific Information initiated the foundation of the Consortium of Libraries in Serbia for common acquisition (KoBSON), which facilitated access to the huge foreign electronic databases and journals.