Nymfaio, originally named Neveska, was settled around 1385 by Vlach travellers, who fled into the mountains after heavy battles with the Ottomans. The fighters remained armed and autonomous, directly ruled by the Sultan’s mother and paid reduced taxes. Around 1630, the village became a centre of silversmithing, known all over the Greek Macedonia region for the next three centuries. During the Albanian incursions in the late 18th century, Nymfaio accepted refugees from various Vlach settlements that were ruined by the raiders.

Rich tobacco and cotton merchants of international magnitude were born and raised in Nymfaio while the village has always been a base to most national struggles as well as homeland to fighters, benefactors and scientists. Nymfaio’s residents actively supported the Greek Revolution of 1821 and at the time the village saw increased activity with gatherings of the Filiki Eteria, an important rebel organization. The ruins of greek war hero Pavlos Melas’ sanctuary and center of operations still exist in the settlement. During the Greek Macedonian Struggle of 1878, the inhabitants of Nymfaio played a significant leading role in the fighting efforts.

By the time of World War One, Nymfaio was a large settlement with over 3,000 inhabitants and 400 children attending the Nikeios School. However, during the Nazi Occupation and the Greek Civil War, the villages around Grammos and Vitsi mountains were deserted. In the 1960s, when the need for work was imperative, the youth left the area to work in the neighboring cities and Nymfaio gradually became deserted with its traditional homes left to ruin.

In 1986, a group of residents of Nymfaio including prominent greek figures like lawyer and journalist Nikolaos Mertzos and winemaker Yiannis Boutaris, following in the footsteps of patriot and local pioneer Nikolaos D. Rozas, decided to breathe new life to the historical village. To that end, they soon became active, sought out to find financiers and proceeded to the reconstruction of the settlement. The old mansions gradually reverted to their original glory, the ruined homes were rebuilt and the alleys turned into elaborate cobbled streets with atmospheric lighting.

Villa Arcturia was built in 1992, at the edge of the settlement, called La Costa. At the same year the large nearby tap was built in order to preserve the supply of cold thermal waters that starts from the mountain’s depths. This water is considered particularly beneficial both for drinking and cleaning use as it has healing properties.