The Ecumenical Patriarch of Constantinople, Bartholomew I, signed the decree of independence, or "Tomos", in Istanbul, formalizing a split that has angered Moscow amid a broader political conflict between Ukraine and Russian Federation.
In a solemn ceremony filled with liturgical singing, the leader of the Orthodox Church, Patriarch Bartholomew I, signed a decree known as a "tomos" that grants autocephaly, or independent national religious authority, to the Ukrainian church.
Metropolitan Epiphanius, head of the newly established Orthodox Church of Ukraine, said that the doors of a single local church are open to all Orthodox Christians.
Ukraine is home to millions of believers who belong to the Orthodox Church, but their loyalties are divided between the Kiev and Moscow patriarchates.
"The pious Ukrainian people have awaited this blessed day for seven entire centuries", Bartholomew said in his address.
The patriarch, considered "first among equals" in Orthodox Christianity, said Ukrainians could now enjoy "the sacred gift of emancipation, independence and self-governance, becoming free from every external reliance and intervention".
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The decree was signed at a landmark ceremony on Saturday, putting the formal stamp on a break with the Russian Orthodox church which has infuriated Moscow.
Now, priests from the Kiev Patriarchate and the Autocephalous Church become members of the new Church - the Orthodox Church of Ukraine. Poroshenko said as he thanked the Orthodox patriarch.
An independent Ukrainian Orthodox church was created at a signing ceremony in Turkey on January 5, formalizing a split with the Russian church it had been tied to since 1686. The Russian church, which now has about 150 million Orthodox Christians under its authority, could lose a fifth of its members.
"Tomos - is just a paper, the result of restless political and personal ambitions".
It had been "signed in violation of the canons and therefore not possessing any canonical force", Legoida added in a statement. In 2014 - more than two decades after Ukraine broke away from the former Soviet Union - Russia annexed the Crimean peninsula and supports separatist rebels in the east of the country.
The Patriarchate of Moscow has more followers than the Patriarchate of Constantinople and has challenged it for authority in the past. "(It) will make Moscow's hope of some future pull of Ukraine back into its "orbit" nigh on impossible without the use of overwhelming (catastrophic) military force".