According to ancient tradition, the monastery was founded in the late 14th century by a repentant robber named Opta, who became known as Macarius in monastic life. A brotherhood gathered around him, and he established the desert, which marked the beginning of monastic life. According to another legend, Optina Pustyn was founded by Prince Vladimir the Brave or one of his descendants who supported monasticism.

There is also a version that previously both monks and nuns lived in the monastery, and such monasteries were called Optina. Exact data on the establishment of Optina Pustyn have not survived.

The first written mentions of Optina Pustyn date back to the reign of Boris Godunov. The Kozelsk land books (1629, 1630, 1631) mention that funds were allocated to the monastery for "candles and incense" in memory of Tsar Feodor Ioannovich. After the Time of Troubles, Optina Pustyn recovered from disasters, including the Lithuanian devastation. The oldest donation book from 1670 contains records of donations from ruling figures.

In 1689, the construction of the first stone church of the Introduction of the Most Holy Theotokos began, with an altar dedicated to St. Paphnutius of Borovsk.

In the 18th century, the material condition of the monastery was dire. From 1704, by decree of Peter I, Optina Pustyn was required to pay a tribute to the state, which was necessary for the construction of St. Petersburg and the war with the Swedes. The tribute proved to be very burdensome for the monastery, and requests to former benefactors testify to its dire situation. By 1724, only 12 people remained in the monastery, and soon it was abolished according to the Spiritual Regulation, merging with the Spaso-Preobrazhensky Monastery in Belev.

At the end of 1726, by decree of Empress Catherine I, Optina Pustyn was restored. In 1741, the construction of a wooden bell tower began, followed by a new church in honor of the Introduction of the Most Holy Theotokos with two altars: the southern one dedicated to St. Paphnutius of Borovsk, the miracle worker, and the northern one to St. Theodore Stratilates.

According to a report from 1770, there were three monks in the monastery, and in 1773, only two, both elderly men.

The state of the monastery significantly improved in 1795 when Metropolitan Platon of Moscow and Kaluga began to pay attention to the needs of the monastery, and just two years later, there were 12 monks in the monastery.

In 1802, the construction of a new three-tiered bell tower, 30 fathoms high, and new wings for the brotherhood's cells began. In 1805, the construction of the Kazan Church started, followed by a hospital church with six cells. Four years later, the number of residents in the monastery increased to 30.

In 1821, a hermitage for hermits was established in the monastery, and the spiritual life began to be led by an elder. People from all walks of life began to come to the monastery, seeking spiritual life, and Optina became one of the spiritual centers of Russia.

Optina Pustyn is associated with episodes from the lives of Kirievsky, Gogol, Dostoevsky, Tolstoy, Solovyov, and other Russian writers and thinkers. V. S. Solovyov brought F. M. Dostoevsky to Optina after a heavy drama, the death of his son in 1877; the writer lived in the hermitage for some time. It is known that some details in "The Brothers Karamazov" appeared thanks to impressions from this trip. The prototype of Elder Zosima was Elder Ambrose, who lived at that time in the Optina hermitage.

On January 23, 1918, by decree of the Soviet government, Optina Pustyn was closed, but for some time the monastery existed under the guise of an "agricultural artel." In the spring of 1923, the artel was closed, and since then, a sawmill, a rest house, the concentration camp "Kozelsk-1," a hospital, and a military unit were located here. Only in 1987 was Optina Pustyn returned to the Russian Orthodox Church. On June 3, 1988, after a long break, the first service was held in Optina Pustyn. Today, the monastery welcomes thousands of pilgrims.