The centuries-old history of Pythio has its roots in antiquity and carries on to the Byzantine and post-Byzantine eras. Together with the neighboring towns of Azoros and Dolichi, Pythio formed the ancient Perraivian Tripolis which, according to Homer, had sent military forces to take part in the Trojan War. Apart from Pythio’s accessible archaeological site, particularly interesting are the hermitages, which are caves in rocks where ascetic monks used to live in seclusion.

The best preserved hermitages are located at the southern slope of Kastri Hill: the hermitage of Ascension (Analipsi), at the foot of the hill, and that of the Holy Cross (Timios Stavros), farther up, have remarkable wall murals which date back to 1339. Also worthwhile visiting is the Church of the Assumption of Virgin Mary (Koimisis tis Theotokou), the village’s cemeteries – sections of which date back to the 11th century- and the rare, due to its circular form, bell tower. Little further up, near the church of Agioi Anargyroi, there is one of the region’s single-arched stone bridges.