In the second half of the 10th century, Polotsk was governed by its own dynasty; its first ruler mentioned in the chronicles was the semi-legendary Rogvolod (?–978), better known as the father of Rogneda.

At the time of its greatest extent, the principality stretched over large parts of present-day northern and central Belarus and a smaller part of today's southeastern Latvia, including (besides Polotsk itself) the following towns: Vitebsk, Drutsk, Minsk, Izjaslaw (now Zaslawye), Lahoysk, Barysaw, Brachyslaw (now Braslaw), Kukenois (now Koknese) and others.

In 862 Polotsk was first mentioned in the Primary Chronicle as a town within the realm of Novgorod Rus', alongside Murom and Beloozero.

He profited from the civil wars in Kiev in order to assert his independence and run the affairs of the principality separately.

During this time Polotsk became a centre of trade serving as a transit location between other lands of Kievan Rus' and Scandinavia.

Most of the time, descendants of Izyaslav ruled the Principality of Polotsk independently of the Grand Prince of the Rus', only formally recognizing the power of the Rurikides.

After the late 10th century, Polotsk was also successful in colonizing the lands of its western neighbours, the ancestors of today's Latvians and Lithuanians.

In the early 13th century, Teutonic knights seized power over the former from the hands of Polotsk, but the historical ties with the latter proved much stronger and lasted for 700 more years, although the leading role in this “marriage” soon shifted to the other side.

The last pagans of Europe, brave and skilful warriors, Lithuanians initially served Polotsk as auxiliary troops in its wars with the Teutonic knights and other East Slavic principalities; but from 1183 they refused obedience to the metropoly and established their state.

After his defeat at the Battle on the river Nemiga and temporary imprisonment, Vseslav died, and the principality was divided between his surviving sons.

However, pagan Lithuanians began consolidating lands of the principality, and in 1240 Polotsk became a vassal of the Grand Duchy of Lithuania.