The illegitimate son of Count Aleksey Kirillovich Razumovsky [ru], who became Russia's Minister of National Education, Perovsky studied at Moscow University, then joined the retinue of Emperor Alexander I in 1811.
As he retreated toward Moscow after the 1812 Battle of Borodino, the French took him prisoner and he remained in captivity until the fall of Paris in 1814.
In 1839 he led an invasion on the Khanate of Khiva – in part to free Russian slaves captured from the Russian frontiers on the Caspian Sea and sold by Turkmen raiders; but also as an attempt to extend Russia's borders in the direction of Central Asia while the British Empire was entangled in the First Anglo-Afghan War of 1839–1842.
Due to poor planning and bad luck, they set off southwards in November 1839 into one of the worst winters in living memory, and had to turn back in February 1840.
His military successes forced the Khanate of Khiva to make concessions in its 1854 treaty with the Russian Empire.