The Byzantine collection links the ancient Greek world to that of modern Greece. The collection is exceptionally rich, although it is not representative of all the different artistic tendencies and currents which flourished during the thousand-year Byzantine Empire, and is divided into two groups.

The first group comprises bronze and silver household and ecclesiastical vessels, miniature sculptures and enamels, ceramics, manuscripts, etc., many of outstanding quality and workmanship. The second group includes Byzantine and post-Byzantine icons, through which the evolution and development of iconography from the Byzantine period and the Palaeologan renaissance can be traced in the workshops of Crete and the artistic production of Mount Athos, up to the early stages of the modern Greek painterly tradition.