The palace was ordered to be constructed in 1744 by the RussianEmpressElizaveta Petrovna, and was designed by Bartolomeo Rastrelli, the most famous architect working in the Russian Empire at that time. One of the students of Rastrelli, Ivan Michurin, together with a group of other architects, completed the palace in 1752. Empress Elizabeth, however, did not live long enough to see the palace. The first royal figure to stay in the palace was Empress Catherine II, who visited Kiev in 1787. In the late 18th and early 19th centuries the palace was the main residence of Governors-General.
In the early 19th century, the palace burned down in a series of fires. Roughly half a century later, in 1870, Alexander II of Russia had the palace reconstructed by the architect Konstantin Mayevsky, using old drawings and watercolours as guide. It was then renamed after the reigning Empress Maria Alexandrovna. By her wish, a large park was established off the southern side of the palace. The palace was used as a residence for visiting members of the imperial family until 1917.
During the years of the Russian Civil War in 1917-20, the palace was used as the Kiev revkom headquarters, particularly during the Kiev Bolshevik Uprising. In the 1920s the building belonged to an agricultural school, soon after which it became a museum. The Mariyinsky was badly damaged in World War II, and restored at the end of the 1940s. Another major restoration was completed in the early 1980s.