It is the most important archaeological museum in Greece and one of the richest in the world concerning ancient Greek art. Its collections are representative of all the cultures that flourished in Greece.

The construction of the museum begun in 1866 and completed in 1889 with the gradual addition of the west wing in 1874, of the north in 1881, of the south in 1885 and finally of the east wing. The building was erected in a large plot donated by Helen Tositsa, with the financial support of Demetrios and Nicolaos Vernardakis, the Archaeological Society and the Greek state.