It is a cathedral church of the Ukrainian Orthodox Church of the Kyiv Patriarchy. It was built in the 19th century (1862-1882). On 20 August, 1896 the cathedral doors opened and the blessing ceremony was held. Russian Emperor Mykola II (Nicholas the Second) was present there. Several architects were commissioned to make the designs and supervise the construction (among them the prominent architect, Academician Beretti). The architectural style is defined as "pseudo-Byzantine-Russian". A group of painters - Ukrainian (Zamyraylo, Sergiy Kostenko, Mykola Pymonenko), Russian (Victor Vasnetsov, Michael Nesterov), Polish (Pavlo Swedomsky and brothers Olexandr and Wilhelm Kotarbinsky) - decorated the interior of the cathedral with murals. In the early 20th century Mykhaylo (Michael) Vrubel, a painter of great distinction, painted four icons for the iconostasis of the church and several frescoes, the best known of which is a big mural, The Descent of the Holy Spirit upon the Apostles.

Before the Mykhailivsky Zolotoverkhy (Golden-Domed) Cathedral was destroyed by the Bolsheviks in an act of atheistic vandalism in the thirties, the relics of St. Barbara, a martyr of the 3rd century AD, were transferred to St. Volodymyr's Cathedral where they have been kept ever since.

The Saturday and Sunday services in the cathedral are conducted by the Patriarch of Kyiv and of all Rus-Ukraine Filaret (Denysenko), who was the Protector of the Ukrainian Orthodox Church of the Kyiv Patriarchy before the enthronement of a new primate (head) of independent Ukrainian Orthodox Church - Epiphanius. Regular services are held every day. During the Patriarch's services, a wonderful choir, made up of National Opera singers, sings in St. Volodymyr's.