Olympios entered Filiki Eteria in 1817, taking the high rank of "Shepherd". He initiated many others in the Eteria, and established contacts with the Wallachian Pandur Tudor Vladimirescu, who led the parallel uprising of 1821. Olympios married Čučuk Stana, the widow of Hajduk Veljko, who had arrived from Serbia to participate in the Greek War of Independence as a fighter, alongside his own men. They had three children: sons Milanos and Alexandros and daughter Euphrosyne.