On July 13, 2006 it was placed on UNESCO's World Heritage List as an extension of the Visoki Dečani site which was overall placed on the List of World Heritage Sites in danger.
Archbishop Arsenije I built the Church of the Holy Apostles, as he wanted the seat of the Serbian Church to be at a more secure location and closer to the centre of the country. Soon, around 1250, he ordered it decoration. Archbishop Nikodim I built the Church of Saint Demetrius around 1320, north of the other church. A decade later, around 1330, his successor, Archbishop Danilo II built a third church, south of the original one - the Church of the Holy Virgin Hodegetria to the south of which he added the small Church of Saint Nicholas. In front of the three main churches, he then raised a monumental narthex. In front of the narthex he built a tower. In the time of Archbishop Joanakije II, around 1345, the hitherto undecorated Church of Saint Demetrius was decorated with frescoes.
During the 14th century, small modifications were made to Church of the Holy Apostles, so some parts were decorated later. From the 13th to the 15th century, and in the 17th century, the Serbian Patriarchs and Archbishops of Peć were buried in the churches of the Patriarchate.