The village of Tolstoshyevo is first mentioned in the census books of the Meshchovsk district in 1646. In 1660 and 1668, these lands belonged to the boyar Ilya Danilovich Miloslavsky, the father-in-law of the tsar. After the death of his widow, Aksinya, the village was owned by the Obukhovs until it was acquired in 1721 by the large industrialist N. N. Demidov.

Demidov renamed the settlement to Bryin-Zavod, built a dam on the Bryin River, and opened an ironworks in 1725. He also arranged the estate, erecting a stone two-story house with 26 windows and an arched entrance to the courtyard. In 1736, he built a wooden church, consecrated in the name of the Transfiguration of the Lord.

According to the "Description and Alphabets to the Kaluga Atlas," in 1782, the village of Tolstoshyevo, known as "Bryin Iron Works," belonged to A. N. Demidov. The village had 224 households, a pond, a wooden church of the Transfiguration of the Lord, a stone manor house, and two gardens. On the Bryin River, there was an ironworks with five hammers, each equipped with two forges for processing cast iron into iron. The village also had two mills: a sawmill and a flour mill.

After the death of A. N. Demidov, the factory came under state guardianship and was sold to the Kaluga merchant Ilya Nazarovich Korobov, who in 1818 transferred it to the ensign of the guard P. E. Demidov. In 1820, Ekaterina Alexeyevna Ryabina, the wife of a state councilor, acquired the estate lands and received permission to close the factory, which had long ceased to function. She rented the factory buildings to the Moscow merchant P. M. Alexandrov for the organization of a cloth manufactory.

In the 1830s, the Bryin cloth factory became a leader in cloth production in the Russian Empire. In 1846, with the funds of benefactor P. M. Alexandrov, A. M. Ryabinin built a new stone church, and two years later, a bell tower was erected nearby.

In 1862, the estate and factory passed to the sons of Ryabina, Mikhail and Alexei, as well as to daughter Varvara Andreyevna Tolstaya, who became the sole owner after the death of her brothers.

After the reform of 1861, the village became the center of the Bryin volost. In 1865, a zemstvo school was opened in the village, and 26 years later, a single-class church parish school was established. In 1881, the Bryin factory closed due to competition from Polish enterprises.

After the death of V. A. Tolstaya, the property passed to her children Alexander Vladimirovich and Natalia Vladimirovna. In 1910, the writer M. M. Prishvin moved to Bryin with his family.

After the revolution, the village of Bryin became a collective farm. During the Soviet era, the estate buildings were used for economic purposes until they fell into disrepair.