The National Library forms part of the so-called "Neoclassical Trilogy" of the City of Athens: Academy - University - Library.

It consists of three solid parts, out of which the one in the middle -which is also the biggest- houses the Reading-Room. To enter this part, one has to pass through a Doric-style row of columns (designed after the Temple of Hephaestus in the Ancient Agora of Thission, which served as its model), after climbing on a monumental curved double staircase of a Renascence style. The Reading-Room, surrounded by Ionian-style columns, is covered by a glass ceiling. The cast-iron constructions of the bookstands were referred to as exceptional back in their time. In general, the building is considered to be a characteristic sample of mature Neoclassicism.

It was built between 1887 and 1902, based on a study of the Danish architect, Theophile Hansen -brother of Cristian Hansen. Hernest Ziller was the supervising architect who also studied the entrance stairways and the main bookstands. As early as in 1858, King Otho had ordered Hansen to make a study for the construction of a Library next to the University, that had already started being built.

The first public Library in Greece was founded in the island of Aegina in 1829 by the then Governor I. Kapodistrias and in 1834 was moved to Athens where, before ending up to the University building, it had been temporarily housed in various old buildings. In 1884 the then Prime Minister Charilaos Trikoupis took the final initiative in constructing the Library, with donations offered by Panagis Vallianos, a Greek national living in Russia and by the Public Endowment Fund, which helped to finish the project.