In mid-September 1814 in Odessa, three Greek merchants, two from Epirus and one from Patmos, decided to prepare the ground for the outbreak of the Greek revolt within the Ottoman Empire 'in due time'. This decision led very quickly to the foundation of the Philiki Etaireia. This society was part of the wider national and revolutionary activity which developed from the late 18th century, especially among the scholars and merchants of the Greek communities of the Diaspora. Its founders were Nikolaos Skouphas, Athanasios Tsakaloph and Emmanouil Xanthos. In the past they had participated in other secret revolutionary societies as well as in Masonic lodges. This experience was useful in the organization and conspiratorial ways of the Philiki Etaireia. Until 1818, the year in which the three founders settled in Constantinople, the Philiki Etaireia was an organization with few members and complex initiation procedures, conspiratorial rules and numerous secret symbols. It is considered that until that time the number of the initiated members did not exceed thirty, mainly eminent Greeks from Russia and the Danubian principalities. From 1814-1818, Anthimos Gazis, a priest and scholar of acknowledged prestige, was included in the leading cell, the so-called Archi of the Philiki Etaireia.

The transference of the society in Constantinople coincides with the death of N. Skouphas and the expansion of the leading group which now included the metropolitan Ignatius of Hungaro-Walachia, the Phanariote Alexandros Mavrokordatos and the archimandrite Grigorios Dikaios (Papaflessas). Furthermore, in the period 1818-1820, the Philiki Etaireia changed its organization, with new members and the specification of a plan for the outbreak of the Revolution. It adopted the so-called system of the twelve apostles. According to this system, twelve honourable members of the Philiki Etaireia were sent in twelve regions where Greek populations lived. The objective of the Philiki Etaireia was to approach local agents with social, political or economic standing. In this period the most important local notables and bishops of the Peloponnese, as well as many klephts and armatoles from Rumeli, were brought into its ranks. At the same time, the four ranks of members under the Archi were increased to six and the initiation ritual was simplified. In addition, Ioannis Kapodistrias was asked to become the leader of the Philiki Etaireia. After his refusal, members approached Alexander Ypsilantis, who accepted the leadership in April 1820.