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In 1990 with the onset of Perestroyka he returned to Ukraine and became Bishop of Uzhgorod and Vynohradiv. For a short period, he was Archbishop of Lviv and Sokal. In 1993, by the decree of Patriarch Mstyslav (Skrypnyk) he was excommunicated for accepting ordination from Metropolitan Filaret (Denysenko).
On October 14, 1993 he was elected Patriarch of the Ukrainian Orthodox Church - Kiev Patriarchy.
On July 14, 1995 Patriarch Volodymyr (Romaniuk) suddenly died under somewhat mysterious circumstances, with the official diagnosis being causes related to a heart attack. His burial took place on July 18, 1995. Many religious and faithful called the day of burial black Tuesday, because of confrontations that took place between members of the clergy, laypeople of different denominations and the nationalist militia battling riot police, after an unsuccessful attempt to have him buried on the premises of the Saint Sophia Cathedral in Kiev. At least two people were killed, dozens more injured. Volodymyr Romaniuk was succeeded by Metropolitan Filaret Denysenko who was enthroned as Patriarch of Kiev and All Rus’ - Ukraine on October 22, 1995.