The Smolensk Cathedral is located at the intersection of the former streets of Nikolopeskovskaya (now Normandie-Niemen) and Smolenskaya (now Mayakovskaya). Despite losing part of its original appearance, it continues to please the eye and, thanks to its favorable location, is visible from many points in Oryol, remaining an architectural dominant of the city.

The first Smolensk church was laid in 1767 by the residents of Streletskaya sloboda with the blessing of Bishop Tikhon (Yakubovsky) from Sevsk and Bryansk. The residents of the sloboda, exiled here by Peter I after the rebellion of 1698, were mostly Old Believers, but in Oryol they began to attend the churches of the official Church. Due to the distance of the sloboda from the city center, there arose a need to build a church, especially in the context of the active activities of the schismatics without priests, whose prayer house was nearby.

Under Catherine II, there was an unofficial ban on the construction of new churches, but the archpastor justified the need for a new church by the mission among the Old Believers and opposition to the schismatics. The Empress allowed the construction of a stone church in honor of the Smolensk Mother of God on the land of Ivan Chepakhin in the center of the sloboda.

The church was oriented with the altar strictly to the east, as is customary in Orthodox tradition. The allocated land was enough for the church, a separate bell tower, and a garden, where later a new Smolensk church was built. The first church was destroyed in the early 1940s, and a cinema called 'Komsomolsky' later appeared in its place.

The main church expanded with chapels and in its final form had three altars: in the name of the Smolensk Icon of the Mother of God, the Uncreated Image, and St. Demetrius of Thessalonica. By 1777, services were already being held in the church. The construction was carried out under the guidance of the elder Ivan Yelenin with funds from the parishioners, who also donated for the decoration of the church. In 1852, the 'Oryol Provincial Gazette' published the will of merchant Ivan Serebrennikov regarding the allocation of funds for the construction of a new church.

The church's relics included the icons of the Smolensk Mother of God and the martyr Mina of Alexandria. The church is mentioned in the works of N. S. Leskov 'The Trifles of Hierarchical Life' and 'The Cathedral Members'.

The church project was developed by architect Efimov in 1856, and the laying was consecrated in 1857. In 1869, the Oryol chronicler G. M. Pyasetsky was married in the church. The main church was completed and finished in 1889, consecrated in 1895, and the bell tower was erected in 1908. In 1899, a school for needy parishioners opened at the church.

In 1938, the church was closed, and during the German occupation, it was used as a bomb shelter. In 1951, the remains of the bell tower were dismantled, and until 1995, a bread factory was located in the church.

In April 1994, the church was transferred to the Oryol-Liven Diocese. On August 10, 1995, after a solemn service and procession, the church reopened. In April 1998, a new altar of the Uncreated Savior, created according to the design of A. I. Kaveshnikov, was consecrated. The left altar was consecrated in the name of St. Demetrius of Thessalonica. In May 1998, an Orthodox metal cross was made for the main dome. In December 1999, the work on the gilding of the dome and cross was completed. In 2014, the interior painting of the church was carried out, and in 2015, a new iconostasis was installed.