The Pokrovsky Cathedral, built in 1689, is a vivid example of a three-part temple that combines elements of Ukrainian wooden architecture and the architectural traditions of Russian churches. Initially, the cathedral had a separate bell tower connected to the main building by a gallery. The lower tier of the bell tower was made of brick, while the upper tier was wooden with a baroque finish. In the first half of the 18th century, the bell tower was rebuilt: the wooden tier was replaced with brick, and a refectory was added, connecting the cathedral and the bell tower.

The architectural composition of the cathedral is based on the scheme of a Ukrainian three-log church. The influence of 17th-century Russian architecture is noticeable in the details of the plan, brickwork, and facade decoration.

The cathedral was erected at a site where the fortress wall approached a cliff above the Lopan River. The bell tower, with its strong walls and narrow loophole windows, was part of the defensive fortifications of the Kharkiv fortress.

In 1843, the hero of the Patriotic War of 1812, V. V. Orlov-Denisov, was buried in the cathedral's crypt. During the Great Patriotic War, the cathedral was damaged but was restored. In the Soviet years, it continued to function as an Orthodox monastery and was recognized as a valuable monument of 17th-century Ukrainian architecture, being the oldest stone building in Kharkiv.

In 1751, the monastery housed 11 hieromonks, 4 hierodeacons, and 10 monks, some of whom taught at the Collegium. The rector of the Collegium was also the abbot of the monastery and wore distinctive insignia similar to those of archbishops.

The curriculum of the Collegium was based on the plan of the Kyiv Academy and included mathematics, history, geography, as well as foreign languages. In 1768, additional classes in applied sciences and arts were opened. In 1789, they were merged with the People's School and renamed the Sloboda-Ukrainian Gymnasium.

Among the teachers and graduates of the Collegium was Hryhorii Skovoroda, a monument to whom is installed by the monastery wall. The monastery library housed rare books, including the Ostrog Bible and other valuable editions.

In 1786 and 1788, during the secularization of church properties, the monastery's estates were confiscated. After the establishment of the Sloboda-Ukrainian Diocese, a Spiritual Consistory was opened on the monastery's territory, and the upper church served as the cathedral until 1846.

By the end of the 19th century, the burial vault under the lower church was expanded and transformed into the Church of the Three Holy Hierarchs. In 1844, the main shrine of the monastery became the Ozerianska Icon of the Mother of God. In 1896, the Ozerianska Church was consecrated, built in a basilica form with Byzantine-Russian decor.

In 1922, the monastery was closed, and its buildings were used by other organizations. In the 1950s, restoration of the Pokrovsky Cathedral began, but the restoration project was completed only in the 1990s. In 1990, the monastery buildings were returned to the church, and in 1992, an Archpastoral Council of the UOC took place here.

By 2003, the restoration of the Pokrovsky Cathedral and the Ozerianska Church was completed, restoring the 19th-century annexes. Commemorative signs were installed in front of the Archpastoral House in honor of the 2000th anniversary of the Nativity of Christ and the 200th anniversary of the Kharkiv Diocese.