The church in the village of Klyavlino was built in 1896 thanks to the efforts of parishioners and the support of the Samara diocesan committee of the Missionary Society, which also allocated funds. This construction was part of Bishop Guriy of Burtas's program aimed at enlightening the Volga peoples with the light of the Christian faith. The church, designed for 500 people, was wooden, standing on a stone foundation, covered with iron, and was unheated. Next to it was a wooden bell tower. There was one altar, dedicated to the holy great martyr Demetrius of Thessalonica, and its consecration was performed on April 10, 1898, by the archpriest of the 4th district of the Buguruslan county, priest I. M. Bogolyubov from the village of Smolkovo.

Until 1900, the church functioned as a "church-school." It had one priest and one psalmist on staff, for whom houses were built in 1899. There were also a watchman's lodge, a prosphora house, and a bathhouse for the clergy. In 1912, the parish library had 160 volumes. The issue of land fragmentation among the parishes was relevant during the synodal period, and the Klyavlino parish exemplifies this well. The lands allocated by rural societies were not always suitable for use. In Klyavlino, the church land was divided into three fields of 11 desyatins each, which turned out to be inconvenient. In 1914, the church's clergy noted in their report: "Of the 3 fields, two should be considered unsuitable for cultivation due to their proximity to peasant pastures, which always suffer from grazing."

In 1898, a one-class mixed church-parish school opened in Klyavlino. In 1902, a similar school appeared in the village of Petropavlovsk. The school buildings were wooden, covered with iron. In 1912, there were 62 boys and 25 girls studying in both schools. The parish included three settlements. The population of the village of Klyavlino was mixed, predominantly Chuvash and Mordva, with only 40 households of Russians. The villages of Petropavlovka and Alexandrovka were purely Russian in ethnic composition. In addition to peasants and clergy, there were 44 merchant households in the parish.

In 1900, Gavriil Ivanovich Perepyolkin, a descendant of Chuvash peasants, was appointed as the priest in Klyavlino. From 1883 to 1893, he worked as a district missionary of the 3rd archpriest district of the Bugulmin county under the Samara diocesan committee of the Missionary Society, baptizing 63 pagans. In 1884 and 1893, Father Gavriil held the position of observer of church-parish schools in the same district. On August 22 and 28, 1899, he participated in a congress of figures in indigenous education in Samara, which gathered priests and teachers from the Volga dioceses. He was assisted in his educational work by psalmist Feodot Petrov, also an ethnic Chuvash.

After its closure in the 1930s, the church remained empty for some time. During the Great Patriotic War, it was converted into an orphanage for refugees from Ukraine and Belarus. After the war, the building was used as a club until 1987. Only in 1990 was the church returned to the believers.