A mediĉval document of ca. 850, called Bavarian Geographer after its anonymous creator, mentions the Slavic tribe of Wolinians who then had 70 strongholds (Uelunzani civitates LXX). The town of Wolin was first mentioned in the 10th century. Archaeologists believe that in the Early Middle Ages there was a great trade emporium, spreading along the shore for four kilometers and rivalling in importance Birka and Hedeby.

Archaeological finds on the island are not very rich but they dot an area of 20 hectares, making it the second largest Baltic marketplace of the Viking Age after Hedeby. Some scholars speculated that Wolin may have been the basis for the semi-legendary settlements Jomsborg and Vineta. This is dubious, as "no trace has been found there of its artificial harbour for 360 warships, or of a citadel, unless the nearby hill of Silberberg is accepted as the site of such; but there were Norsemen there around the year 1000, and the archaeological finds reveal a mixed population of Scandinavians and Slavs".

Around 972 the island became controlled by Poland, under prince Mieszko I, however, it has not been established if Wolin became part of Poland, or if it was a fief. Polish influences were not firm and they ended around 1007. In the following years Wolin became famous for its pirates, who would plunder ships cruising the Baltic. As a reprisal, in 1043 it was attacked by the Danish king Magnus the Good.

In early 12th century the island as part of the Pomeranian duchy was captured by the Polish king Boleslaw III Wrymouth. Shortly after the inhabitants of Wolin accepted Christianity, and in 1140 pope Innocent II created a diocese there, with capital in the town of Wolin. In 1181 the dukes of Pomerania decided to accept the Holy Roman emperor as their liege lord instead of the Polish king. In 1535 Wolin accepted Protestantism Lutheranism. In 1630 the island was captured by Sweden. Later Pomerania became part of the Prussian (at that time Brandenburgian) kingdom. Wolin followed in 1679. Since the German political unification in 1871 it was part of Germany. After the transfer of Western Pomerania to Poland in 1945 the (German) population was expelled and replaced with Poles who had been expelled from territories in eastern Poland ceded to the Soviet Union.