The population of the town was 3021 inhabitants while that of the entire municipality 5597, according to the 2001 census.
Historically, Molaoi have been inhabited since the pre-Mycenean era. The actual name "Molaoi" first appears in the Byzantine era, in a letter written by emperor Andronicus II in 1292. It is said to derive from the word μύλος (mill).
During the Turkish rule of Greece, Molaoi had a small number of Turkish settlers. They fled when the town was liberated on March 23, 1821, in the Greek War of Independence. In September 1825, the town was destroyed by the army of Ibrahim pasha.
In modern times, the town's population decreased due to migration. Its remaining inhabitants are mostly farmers.
Among the town's facilities are: a public library, a hospital, fire station, police station, high school, etc. Many of these have been built with contributions from former Molaoi residents who migrated abroad.