The Library was established under the patronage of Jevrem Obrenović through an oral proclamation in a formal gathering attended by distinguished figures both from the secular and ecclesiastic realms. On that occasion, Miloš Obrenović entrusted a book to its care.

As part of the Typography Establishment of the Principality, the Library was relocated to Kragujevac and then returned to Belgrade.

The book collection of the Typography Establishment of the Principality came under the authority of the Ministry of Education.

During this period, the Library was referred to by various names: Ministerial Library, Local Library, National Local Library, Serbian Library, Serbian State Library and Library of the Ministry of Education.

Filip Nikolić was appointed as the first librarian. He compiled a comprehensive alphabetical catalogue of the Library’s holdings and proposed the initial budget for the procurement of materials and book binding. He also advocated for book storage facilities.

The Library obtained its first reading room, following its relocation to the building that belonged to Miša Anastasijević (known as Captain Miša's Mansion).

The Law on Printing mandated the submission of legal deposit copies to the National Library.

Stojan Novaković advocated for the separation of the Library and the Museum (established in 1844) from the Ministry of Education within the budget for the year 1871. The Library thus became an independent entity under the direct management of the librarian.

By the Law on the National Library and Museum, the two institutions became completely independent.

By the Law on the Academy of Sciences, the Academy was mandated to oversee the Library’s work, a responsibility it held until the conclusion of the Second World War.

The National Library instituted Rules Governing Internal Organisation and Operations, covering all work aspects in detail.

The Law on the National Library, along with the Rules Governing the Internal Organisation and Operation of the National Library, marked a turning point. This legal framework resulted in an increase in the number of employees and the scope of book procurement activities. The Library's tasks were defined as follows:

1. aiding the advancement of science in Serbia,
2. facilitating broader public education,
3. working on the Serbian bibliography.

Affected by the war, including damage from bombings, the National Library relocated sections of its collections to Niš and subsequently to Kosovska Mitrovica. The rest of the materials were distributed across Belgrade. The collection that had been moved to Niš was taken to Sofia by the Bulgarians but was eventually returned after the war.

Following the war, some materials were irretrievably lost, including 3,132 books, 4,177 magazine volumes, virtually all newspapers from 1914 and 1915, 138 significant letters, as well as all inventories and catalogues. The Library also lost its building.

The new Law on the National Library transformed it into the Central State Library, granting it the authority to receive legal deposit copies from the entire territory of Yugoslavia, which was then known as the Kingdom of Serbs, Croats and Slovenes).

The building of a cardboard factory owned by Milan Vapa, at the address of Kosančićev venac 14, was purchased for the Library.

The Library got its first female librarian – Ljudmila Mihajlović.

After years of organising its collections, the Library opened its doors to readers.

Regulations on the State Qualifying Examination for the National Library were introduced.

The Yugoslav Librarians’ Association was established.

The publication of the Library journal (Glasnik Narodne biblioteke) commenced, featuring professional articles alongside the Current Yugoslav Bibliography.

In the Belgrade bombing of 6 April, both the Library's collections and its building were razed to the ground. This resulted in the loss of 500,000 book volumes, 1,424 Cyrillic manuscripts and charters, 4,000 magazine titles, a total of 1,800 newspaper titles, cartographic and graphic collections, the archive of Turkish documents on Serbia, the entire correspondences of significant figures and all inventories and catalogues.

To restore the Library's holdings, the Ministry of Education decided to allocate rare materials from other libraries to it, including the complete Royal Library and Senate Library and portions of the National Assembly Library and St. Sava Society Library collections. Also, many domestic and foreign libraries, and individual citizens, donated their materials. The Library was also able to purchase some collections.

The library was placed in the adapted building of the Srpska kruna hotel.

The Author Catalogue was established in 1947, followed by the Subject Catalogue the next year.

The Department for Supplementary Collections was established, which later evolved into the Department for Special Collections.

The Executive Council of Serbia made a decision to construct a new building.

The Statute of the National Library of Serbia outlined the internal organisation and management structure of the Library.

The Law on Serbian Libraries granted the National Library a distinctive role as the state’s central library, endowing it with a range of important responsibilities.

The new Library building, with 10 reading rooms and a total of 500 seats (constructed following the design by architect Ivo Kurtović), ceremoniously opened its doors to the public on 6 April 1973.

The Specialised Catalogue by Universal Decimal Classification (UDC) and the Serbian Central Catalogue were formed.

The library transitioned to processing monographic and serial publications according to the International Standard Bibliographic Description (ISBD).

Coordinated book procurement for central libraries commenced.

The library began cataloguing publications before their release – CIP (Cataloguing in Publication).

Mutual cataloguing was introduced across the network of Yugoslav libraries, and the YUBIB database was established.

The Electronic Catalogue of the National Library of Serbia was formed.

This period marked the first attempt at automating user-related processes, including user registration, publication ordering and returning.

Work on a new computer system for library material processing began.

Printing of catalogue cards was discontinued.

Painters and sculptors donated 140 works to the Library.

A local computer network was set up, connecting the library's computers into a system and enabling internet access from all available devices.

The first Library website was created.

KoBSON (Consortium of Libraries for Unified Acquisition) was established within the Centre for Scientific Information. KoBSON provides web access to electronic journal databases.

The Virtual Library of Serbia (VBS) project was launched, which involved constructing a mutual cataloguing system with a central electronic catalogue and a network comprising all libraries in Serbia.

A new website was developed.

A strategic document outlining digitisation priorities was adopted, and the Digital Library Department was founded. It was the only such department in the entire country.

The user area of the building underwent reconstruction. The National Library of Serbia obtained 600 reading spots, 13 reading rooms, 150 user computers, wired and wireless internet access, a section for the blind and visually impaired equipped with all the necessary technology, a Multimedia Reading Room and an Electronic Reading Room.

E-lending was introduced. Since then, all monographic publications available in the electronic catalogue can be ordered electronically.

The National Library of Serbia established its presence on social media platforms: Instagram, Facebook and Twitter.

The National Library of Serbia launched a new website.