Metropolitan Onufriy, 69, the former head of the church in Chernivtsi and Bukovyna in southwest Ukraine, succeeds Metropolitan Volodymyr, who died last month.
Ahead of the vote in Kiev, President Petro Poroshenko emphasized the "patriotic potential of the church," saying that the election took place "during the most difficult period in Ukraine's history as blood flows and we suffer from external aggression."
"In these circumstances, the unifying role of the Church and its educational and patriotic potential are extremely important," he said in a statement.
Orthodox Christians make up the largest denomination in Ukraine but the faithful are split between two main Ukrainian Orthodox Churches -- one loyal to the Moscow Patriarchate and the other to the Kiev Patriarchate.
The Moscow-linked one is believed to be the largest, with more than 11,000 parishes, although it operates as a semi-autonomous Church that has resisted calls to return to the full jurisdiction of the Moscow patriarchate.
The new leader was chosen over two rounds of voting and also received the blessing of the Russian Patriarch Kirill, who has openly supported Kremlin strongman Vladimir Putin.
By Ruchi Singh
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