The liturgy was led by Head of the Ukrainian Orthodox Church (the Moscow Patriarchate), Metropolitan of Kyiv and All Ukraine Onufrii, Censor.NET reports.
Some faithful had to climb up the hills to catch a better view of the service.
Except for the national guards, the security at the event was provided by representatives of Cossack and religious NGOs.
The liturgy was attended by Opposition Bloc MPs Vadym Novinskyi, Nestor Shufrych, Yurii Boiko and some former Party of Regions members.
Former Yanukovych's allies had some sweet talk with Superior of Kyiv Pechersk Lavra, Metropolitan of Vyshhorod and Chornobyl Pavel.
In an interview with one of the TV channels, Shufrych said that the people who came to St. Volodymyr Hill "exercised their right to worship Saint Volodymyr and take part in a prayer for Ukraine."
Several men, wearing striped vests and black glasses, accompanied the Opposition Bloc MPs during the service.
Metropolitan of Kyiv and All Ukraine Onufrii has arrived at St. Volodymyr Hill.
After the service was over, the worshipers set for the Kyiv Pechersk Lavra monastery. The column stretched for more than 3 kilometers. According to some estimates, the march was attended by more than 20,000 people.