In 1852, Metropolitan Philaret of Moscow suggested a large cathedral should be built in Kyiv to commemorate the 900th anniversary of the baptism of Kyivan Rus' by prince Volodymyr the Great.

People from all over the Russian Empire started donating to this cause, so that by 1859 the cathedral fund had amassed a huge sum of 100,000 rubles.

The design was executed in neo-Byzantine style initially by the architects I. Schtrom, P. Sparro, R. Bemhardt, K. Mayevsky, V. Nikolayev.

The painting of the Holy Mother of God by Vasnetsov in the altar apse of the cathedral impresses by its austere beauty.

The relics of Saint Barbara, a martyr of the 3rd century AD, were transferred to St Volodymyr's from the St. Michael's Golden-Domed Monastery before it was destroyed by the Bolsheviks,[3] and have remained there since.