According to the 14th-century account of Patriarch Evtimiy, the church and the surrounding monastery were built on the order of Tsar Ivan Asen II's (ruled 1218–1241) wife Anna.

After the Fall of Tarnovo to the Ottomans in 1393, the church may have become the seat of the Bulgarian Patriarchate for a brief period.

It continued to be a metropolitan bishop's residence of the Ecumenical Patriarchate of Constantinople during the Ottoman rule.

The earliest layer consists of three images of the martyrs of Edessa in the western arch dating to the mid-13th century.

The second layer is the images in the narthex; it is stylistically influenced by the Italo-Cretan school from the time of the Council of Florence in the 1430s.