Tolvui, one of the oldest Zaonezh pogosts, has mentions of Orthodox churches dating back to 1718. Three wooden churches stood on this site: a tent-roofed church of the Holy Life-Giving Trinity with one dome, a tent-roofed church of St. George with five domes, and an octagonal church of St. Nicholas the Wonderworker with eleven domes. All of them burned down in 1722. In 1751, two new churches were built on the same site: the Trinity Church with an altar dedicated to the venerable Zosima and Savvatiy, and the George Church. The Holy Trinity Church burned down again in 1794 but was soon restored with a refectory, as was customary in other churches. In 1796, Tolvui became the center of a parish with a population of 2,590. The parish mainly consisted of small villages located 7, 10, and 15 versts away from the pogost. On June 2, 1845, both churches burned down due to a lightning strike.

In 1848, a wooden single-altar church in honor of the Holy Life-Giving Trinity was built. Its fate remains unclear, as there are conflicting reports. According to some sources, the church burned down due to the negligence of church watchmen, while others state it was closed during the Soviet era.

The idea of building a stone church arose thanks to His Eminence Arkady, Archbishop of Olonets and Petrozavodsk. The Tolvui priests wanted to create a three-altar church to restore the altars of the ancient churches. It was decided to build a church in honor of St. George the Great Martyr with altars in honor of the Sign of the Mother of God and the venerable Zosima and Savvatiy. However, this desire did not align with the opinions of local wealthy individuals, who wanted a single-altar church. Construction began but was halted after the death of the senior priest A. M. and the retirement of Archbishop Arkady. The construction stood for several years until the architect rejected it. After revising the plan and reducing the size, a single-altar church was built and consecrated on July 25, 1876, by Bishop Ionafan.

In 1863, one of the first rural parish schools in the district was opened at the pogost.

During the Soviet era, the church of St. George the Victorious was closed, and its domes and bell tower were destroyed. In the 1940s, the domes were demolished, and in 1985, the church burned down, likely as a result of arson.