In 1820 he joined the Filiki Eteria and since then he started to lay the groundwork for the beginning of the revolution in Central Greece. Around the same time he met with Athanasios Diakos who decided to halt the Ottoman advance into Roumeli by taking defensive positions near Thermopylae. During this battle (Battle of Alamana) Dyovouniotis defended the bridge of Gorgopotamos. However, the battle was lost and Diakos was impaled.