The collection of historical documents includes documents dating from the Byzantine era, the Ottoman era, documents from the "Filiki Eteria", the Greek Revolution of 1821, the Greco-Turkish war of 1897, the Macedonian Struggle, the Balkan Wars (1912-1913), the Greek Civil War, the Asia Minor campaign and catastrophe, World War II, the German/Italian occupation, the Cypriot struggle for the unification of Cyprus with Greece (1955-1958), as well as documents from Greece's political life until today.

The Museum's documents archive covers a period of many centuries.

Aside from special and chronologically classified categories, the following documents are especially important for Greece's history, dating from the period of the Greek Revolution:

-An original, hand-written Proclamation of the Revolution of 1821 against the Ottoman Empire, written by members of the "Filiki Eteria" –the secret society that organized the Revolution. This belonged to George Tzanos, an ancestor of the Faltaits family, who was a close partner and confidant of Alexander Ypsilantis, leader of the "Filiki Eteria".

-The Renouncement (or Excommunication) of the Greek Revolution by Patriarch Gregory V, which was signed by all members of the Church Congress. It is a rare document regarding the history of the 1821 Revolution.

-A Ferman by the Sultan which gave the Skyrians the privilege of preserving their property, religion and language as well as their right of self-government, after the Turks occupied Skyros in 1538.

-A letter by the Cleric and Educator Neophytus Vambvas to the National Benefactor Ioannis Varvakis (1820)

-A document by Augustine Kapodistrias to George Grimaldi, an ancestor of Anna-Marcello-Faltaits (1829).

The collection also contains:

-manuscripts from the Byzantine period
-documents from the Ottoman period -most of which dating from the 17th century to the Greek Revolution of 1821

-documents regarding Skyros' affairs,
-manuscripts, journals and memoirs of Demetrios Faltaits, containing valuable information about Odessa, Tangarog (former Russia) and Ismir and the life of Greek communities in those cities during the 19th century

-Konstantinos Faltaits' archive of published and unpublished documents regarding the Asia Minor Campaign and Catastrophe

-Manuscripts of short stories and poems written by the famous Greek author Alexander Papadiamantis, which were given to Konstantinos Faltaits by the author's sisters after his death.

-The archive of the Greek Student Movement of 1955-1959, in which Manos Faltaits played a leading role.