The Academy of Athens forms part of the so-called "Neoclassical Trilogy" of the City of Athens: Academy - University - Library. It consists of aesthetically distinct parts that form a harmonic ensemble of built mass. A corridor connects the two lateral wings to the main body of the building, which -in its proportions of line and mass- is set-off by its Ionian-style entrance and its big pediment. The entrance has elements originating from the eastern side of Erechtheion, on Acropolis. The predominant material on the facets is marble. Overall, the building is a characteristic example of mature Neoclassicism.

It was built in two phases, in 1859-1863 and 1868-1885, based on studies of the Danish architect Theophile Hansen and it is believed to be his most exquisite work in Greece. Hansen himself was also supervising the construction up to 1861 when E. Ziller took over. The embossed compositions on the central pediment and the statues outside are works of the sculptor L. Drosis. The embossed compositions on the eight small pediments are worked by Fr. Melnizki (1875) and the wall-paintings in the interior were made by K. Grupenckel.

The main donator to finance the construction was the family of the Baron Simon Sinas, Ambassador of Greece in Vienna, Berlin and Munich. In 1887, the architect Hernest Ziller, acting as proxy of Sinas' heirs, delivered the building complete to the then Prime Minister Charilaos Trikoupis.