The border point Kapshticë/Krystallopigi connects Devoll with the Greek regional units of Florina and Kastoria to the east and southeast.

Devoll borders the municipalities of Kolonjë to the southwest, Korçë to the west, Maliq to the northwest and Pustec to the north.

[1][5] Excavations at Tren cave unearthed Mycenaean Greek pottery of the Late Bronze Age.

In a text by Emperor John VI Kantakouzenos (r. 1347-1354) whose 'History' covers the years 1320-1356, there is mention of local Albanians; “While the emperor was spending about eight days in Achrida (Ohrid), the Albanian nomads living in the region of Deabolis (Devoll) appeared before him, as well as those from Koloneia (Kolonja) and those from the vicinity of Ohrid.” This meeting was estimated to have taken place at around February 1328.

[11] During the World War I, the Greek army burned several Muslim villages in the region, including Sinicë (Miras).

[13] The chapel in the Blashtonjë cave on the edge of the Small Prespa Lake dates to the 13th century AD.

In the Communist period, it belonged to the Korçë region, which it was separated from in 1990 as part of the reform of administrative divisions.

The municipality is located in the upper reaches of the Devoll river, which originates in the southwestern part of the area.

As a result of heavy rainfall and spring snow melt, the water flows out of the Small Prespa Lake through a natural outlet, into the Devoll and then directly into the Adriatic.

As a result, the whole region, which is isolated from the rest of Albania, is heavily dedicated to border trade with Greece.

Despite being a primarily agricultural area a large service industry has developed around the border trade.

In particular, many young men of this area worked in Greece in the 1990s, mostly illegally, in order to escape the poverty at home.