The large brick church in the classical style was built on the site of a stone cathedral erected between 1672 and 1681. Its construction began in 1810, the refectory was completed in 1837, and the main church in 1841. The refectory housed altars dedicated to Athanasius of Alexandria and Paraskeva Friday, while the side altars of the main church were dedicated to Stephen and the Mother of God of the Caves.

The main volume of the building was a square with a large rotunda, refectory, and side altars topped with small domes. A separate multi-tiered bell tower in eclectic style was built between 1865 and 1875. The cathedral housed a miraculous icon of St. Nicholas the Wonderworker, carved from wood and revealed in 1415. The church was located at the top of Cathedral Mountain (known in the 17th century as Samorod Mountain) at the confluence of the Mtsna River into the Zusha.

The "House of St. Nicholas" in Mtsensk was one of the oldest churches in the Oryol region and likely existed as early as the 12th century. The first documentary mentions of it date back to 1625. The wooden cathedral was located in the center of the Mtsensk Kremlin, known as the Rubleny City. The Kremlin also housed a wooden church of Paraskeva Friday. In 1672, construction began on a stone cathedral with a bell tower to replace the dilapidated wooden church, which continued until 1681. In 1689, the builder of the church was buried here. In 1757, the cathedral suffered greatly from a fire, which also destroyed the remnants of the wooden fortress and the church of Paraskeva Friday, which was later rebuilt elsewhere. In the same year, the old refectory and bell tower were dismantled, and construction of new ones began. By 1773, a more spacious refectory with an altar in the name of Athanasius of Alexandria and a tall bell tower in baroque style were built.

By the beginning of the 19th century, the old cathedral had become dilapidated and cramped for parishioners. A new project was commissioned from architect Abraham Ivanovich Melnikov. The new cathedral was laid in 1810 on the territory between the old cathedral and the site of the Friday church. In 1837, the warm refectory with two altars: St. Athanasius of Alexandria and St. Paraskeva Friday was completed. The old cathedral was dismantled, leaving only the bell tower, while the new church was expanded with the altars, completed in 1841. In 1844-1845, the cathedral was painted by artists Tikhon and Nikolai Bogdanov. In 1859, the territory was surrounded by a stone fence. In 1865, the construction of a new bell tower began, completed ten years later.

The largest bell weighed 718 poods and was cast at the Smagin factory in Moscow. The bell tower also housed an ancient messenger bell with the inscription: "7188 (1680) February 2, the Great Sovereign's state messenger bell in Mtsensk."

The main shrine of the cathedral was the miraculous icon of St. Nicholas the Wonderworker, which attracted hundreds of thousands of pilgrims annually. According to tradition, the icon arrived in Mtsensk in 1415 on a stone shaped like a cross against the current of the Zusha River. The cathedral attracted the attention of travelers, including Prince I.M. Dolgorukov and philologist I.I. Sreznevsky. N.S. Leskov mentions in his work that his character Levsha went to venerate the miraculous icon before an important task.

The church was blown up in the 1930s, and the remains of its walls stood until the early 1960s. In 1996, to commemorate the 850th anniversary of Mtsensk, a brick chapel was built on its site.