Serbian archbishop Arsenije I (St. Sava's successor), erected the Church of the Holy Apostles and transferred his seat to Pec (Metohija); the church was painted in 1250.

In the complex of the latter Patriarchate of Pec, northward, also was built the adjacent Church of St. Demetrius, c. 1320, by Archbishop Nikodim. His successor Danilo II, the famous Serbian writer, statesman, and even warrior, built yet another temple at the southern end of the Holy Archangels and dedicated it to the Virgin Hodegetria. Somewhat later, he attached to it the little Church of St. Nicholas. Along the fronts of the three mutually adjacent churches, a monumental narthex with a tower in front of it was erected also by Danilo II. In the time of archbishop Joanikije, 1345, the Church of St. Demetrius was painted. In the course of the 14th c. repairs were carried out in the Holy Apostles so that parts of the church were painted later.

Hard times hit the complex during the early Turkish occupation. With the restoration of the Serbian Patriarchate of Pec in 1557, the place regained its focal spiritual and political role. In 1565 the narthex was painted and the iconostasis renovated. The frescoes were refreshed in 1620-21. While patriarch Pajsije held the throne, the Holy Apostles were restored, and in 1633-34. the western part was repainted, for the old frescoes have been seriously damaged. In the time of patriarch Maksim, in 1673-74. St. Nicholas was painted. During the war between the Turks and Austrians, in which the Serbs fought on the Christian side, the patriarchate was badly damaged. The treasury was transported to Gracanica and hidden in one of its domes, however, the Turkish rebel and bandit Jeghen Pasa found it and took it away in 1688: he needed nine horses to load it. In 1690 patriarch Arsenije III Carnojevic had to leave his throne before the Turkish offensive spearheaded by the Tatar and Albanian irregulars, and flee to safety in Belgrade. After the Turks took Belgrade, in October 1690, he had to pass on the Hungarian side and withdraw, with about 30.000 Serbian refugees, to Buda and St. Andrew, a small town near the Hungarian capital. The Turks and Albanians plundered and desecrated the monastery, and also many other Serbian sanctuaries. The Patriarchate was abandoned in another war with the Turks, 1737-1739, when Patriarch Arsenije IV Jovanovic left for Srem, taking along the monks and the valuables. Yet another demolition of the monastery was suffered by the Aslan Pasa of Bosnia in 1831.

The Church of the Holy Apostles is the oldest church within the complex. It had elaborately been planned by St Sava and built accordingly. The oldest parts are its altar and sub-domical spaces, as well as the choirs. Due to the later construction of the adjacent temples, the western end >has not retained the original look. The church was built in stone, plastered, and painted without. The frescoes date from different periods. The earliest, in the altar and under the dome, dates back to the mid-XIII c. Their topical complexity indicates that Sava and Arsenije I had an impact on their theological contents. The frescoes on the south and west walls, probably commissioned by King Milutin, include the portraits of Stefan the First Crowned and Uros I. Two pilasters and the arc connecting them between the west and north bays were presumably painted between 1350. and in 1354. Shortly afterward, because some frescoes had decayed, the choir space was painted too. In those years, the composition of patriarch Joanikije's Dormition was created above his sarcophagus. C. 1620. Georgie Mitrofanovic portrayed Patriarch Jovan in the niche of the west wall. Patriarch Pajsije partially financed the renovation of the deteriorated frescoes in 1636. The Church houses the relics and graves of three archbishops, Arsenije I, Joanikije II, and Sava II.

The Church of St Demetrius was founded by Archbishop Nikodim (1317-1324). Not big in size, it has the form of a shortened cross with a spacious dome. It was built in alternate courses of brick and stone. The entrance is framed with a harmonious stone portal. Joanikije is to be credited for the frescoes painted towards the middle of the 11th c. They were renovated in the early 17th c. They consist of valuable portraits of Emperor Dusan, his son Uros V and Patriarch Joanikije, and also a worthy composition of two Serbian Councils on a vault in the western part. The church houses the relics of patriarchs Jefrem and Sava IV.

The Church of the Virgin Hodegetria was built next to the southern side of the Holy Apostles, c. 1300. It was commissioned by Danilo II, to counterpart the church of St Demetrius. The ground plan has the form of a floral cross with an octagonal dome borne by four free-standing pillars. The temple is partitioned into three longitudinal spaces. Its two-light windows on the east and south facades have certain Gothic elements. The church was painted in the 1330s. The founder's composition on the west wall testifies to the fact that Danilo II had commissioned those works as well.

The narthex was erected by Archbishop Danilo II in the early 1330s, as an ante-church to the three adjacent temples. At first, it was open to three sides, and inside, due to the large span, there used to be five buttresses to carry the whole mass. Since the narthex had gradually deteriorated and became insecure, the arched openings were walled up within the restoration in the 1560s. Little has been preserved of the original frescoes that had adorned the whole narthex in the time of Danilo II. Noteworthy is the genealogy of the Nemanjic Dynasty beginning with Nemanja and ending with King Dusan. Among the individual figures, the representation of the Breast-feeding Mother of God stands out. The facade of the narthex used to be painted, too. Before 1375, above his stone throne, St. Sava was painted on a pilaster in the doorway of the Holy Apostles but signed as a patriarch instead of an archbishop which is his actual rank. Other frescoes on the vaults were painted in 1565, after the renewal of the Patriarchate, commissioned by the Patriarch Makarije Sokolovic, with 365 figures illustrating each day of the Calendar. The painters employed included monk Longin, the most famous Serbian painter of the latter half of the 16th c.

The Church of St Nicholas is a little church, also founded by Archbishop Danilo II. It is a single nave building with a tripartite apse, of brick and stone. The tunnel vault is strengthened by an arch resting on two pilasters. The original frescoes have not survived. The latter painting of the church, in 1673, had been commissioned by patriarch Makarije. The frescoes were created by Radul, the most famous Serbian painter of the late 17th c. The founder's composition on the south wall shows St Nicholas taking Patriarch Makarije to Jesus Christ. On the north wall, there are the portraits of the Serbian saints Simon Nemanja and Sava, as well as archbishops Arsenije I and Danilo I.

The whole Patriarchate of Pec used to be girdled with a wall strengthened with five towers, one of the donjons additionally fortified. Of some monastic facilities, only foundations have survived. The residence at the back of the churchyard was set on fire by Albanian terrorists in 1981; they were restored in 1983. The new residence in the northeastern part of the yard was completed in 1991.

After the Bishoprics of the Serbian Orthodox Church united in 1920, metropolitan Dimitrije was enthroned in Pec as the first Patriarch, after 1766, of the renewed Serbian Patriarchate. Ever since all the elected patriarchs have been enthroned ceremonially in this monastery. The Patriarchate of Pech is a monastery under the administration of the Patriarch himself and exempted from the jurisdiction of the regional bishopric.