The Church of Saint Demetrius of Thessalonica, along with the Sergievsky Church, was one of the oldest church buildings in the city. The first mentions of it coincide with mentions of the Prophet Elijah's church: "The Church of the Prophet Elijah and the chapel of Saint Demetrius of Thessalonica (1615) was located at the confluence of the rivers Livenka and Sosna, overlooking Zalivenka and Belomestnaya Sloboda. It was wooden, dilapidated, and the church contained icons, candles, books, bells, and other church property. It was served by priest Ivan, whose house was located near the Church of Saint Elijah, but there was no land for the church."

Later, the Church of the Prophet Elijah was abolished, and the Church of Demetrius of Thessalonica was moved to the Belomestnaya Cossack Sloboda. The 1615 Supplementary Book states: "In the Belomestnaya Cossack Sloboda, across the river Sosna, opposite the city of Livny, there is the church of Saint Great Martyr Demetrius of Thessalonica, wooden, and in it are icons, candles, and other church property of priest Vasily. This church had the yard of priest Vasily, the yard of deacon Lukyanov Afanasiy, and the yard of the sexton Stepan."

According to the "Census Book" of 1678, the Dmitrievskaya Church survived during the devastation of the city by Hetman Sagaidachny in 1618, but over time it became dilapidated and abandoned. As a result, it was decided to build a new stone church, completed in 1772. The construction was funded by contributions from all the residents of the Belomestnaya Sloboda, and the day of consecration became a holiday for the local residents, entering church history.

The stone Dmitrievskaya Church of Saint Demetrius of Thessalonica had an altar in honor of Saint Demetrius of Rostov. After the consecration of the altar in 1772, priest Peter Turbin and the parishioners asked Bishop Tikhon II of Voronezh and Yelets for permission to hold a procession from the Trinity Cathedral to the Dmitrievskaya Church on the day of Saint Demetrius of Rostov. This was permitted and took place in the early years of the stone church's existence.

The wooden church stood until 1855. In 1841, the construction of a new stone temple began, completed in 1848 with the erection of a three-tiered bell tower in the old Moscow style. There was also a building for the church parish school.

Only legends remain about the beauty of the church's decoration and the church choir, but they are quite interesting. All the icons in the Dmitrievskaya Church were covered with expensive vestments, which made it the first to be plundered.

Like many Russian churches, the Dmitrievskaya Church was marked by martyr's blood: its last rector, Father Gavriil Semov, a man of stern and brave character, was shot in Lipovchik (a locality in the Livensky district) in the 1930s.

The Church of Demetrius of Thessalonica was the last of the city churches destroyed in the 1960s, but the first to be restored in Livny thanks to the efforts of Archpriest Anatoly Bas and the residents of the city from 1999 to 2004.