Ancient Skioni is located on Mytikas, between NeaSkioni and Agios Nikolaos. It is a rather inaccessible hill dominating the area over the sea. Since the slope facing the sea is steep, the access from the South is impossible.

The ancient city was built on the hill in front of the sea, while the northern hill corresponds to the one in front of the town mentioned in Thucydides. It seems that the town was well fortified, since it had been under siege by the Athenians for two years. In the early 20th century parts of a tower on the hill were visible over the fortification. This is where Thucydides locates the acropolis.

A coin from ancient Skioni (approx. 500 B.C.) has an effigy of Protesilaos, the Homeric hero, who is considered the founder of the city. The port of Skioni was a very important factor for the town’s prosperity. Skioni became a member of the Athenian Confederacy in the 5th century B.C., but acceded to the demands of the Spartans during the Peloponnesian War. However, Skioni paid this defection; the Athenians occupied Skioni, slaughtered the citizens or took them slaves and populated the city with Plateans who were forced to leave their homes.