Countess Anna Alexeyevna Orlova-Chesmenskaya, lady-in-waiting, was the only daughter of Count Alexey Grigorievich Orlov and Yevdokiya Nikolaevna Lopukhina. She was born on May 2, 1785, in Moscow. Losing her mother at an early age, Anna remained under the guardianship of her father, who provided her with a secular education focusing on the study of French, German, and English languages. At the age of eight, Anna became a lady-in-waiting, and in 1796, her father brought her to St. Petersburg, where she was presented to the Empress. The change of reign temporarily altered the life of the Orlov family, and Count Alexey Grigorievich went abroad, taking his daughter with him. Upon returning to Russia under Emperor Alexander I, they settled in Moscow, near the Don Monastery. At 16, Anna was praised by the poet Derzhavin for her intellect and soulful qualities. Many noble suitors, including Prince Kurakin and Prince Platon Zubov, sought her hand, but she rejected them. After her father's death in 1807, Anna inherited a vast fortune and decided to live independently, declining her uncle's offer to move in with him. She invited her half-brother, General A. A. Chesmensky, to manage her affairs and refused marriage, although she had feelings for Count N. M. Kamensky, but soon became disillusioned with him and turned to religion.

After her father's death, Anna went on a pilgrimage to Kyiv and Rostov, where she met the elder Amfilokhiy, who became her spiritual guide. After his death, on the advice of Bishop Innocent, she invited monk Photiy to become her spiritual mentor. In 1822, Photiy was transferred to the Yuriev Monastery, which he restored with Anna's support. The Countess bought land near the monastery, built a manor, and moved there, leading a strict monastic life. She transferred the remains of her father and uncles there, which were later moved to the estate of Orlov-Davydov. Anna completely submitted to her spiritual guide, who died in her arms.

Despite her secluded lifestyle, Anna maintained connections with society and the court, receiving favors from the royal family. In 1817, she became a lady-in-waiting, received a portrait of Empress Elizabeth Alexeyevna, and the Order of St. Catherine. In 1828, she accompanied Empress Alexandra Feodorovna on a trip across Russia and abroad. As a large landowner, Anna did not support serfdom and sought to improve the lives of her peasants, freeing them and converting them to Christianity. In her estates in the Samara province, she built a church for the newly converted.

Anna Alexeyevna, possessing robust health, rarely fell ill and passed away suddenly on October 5, 1848, at the Yuriev Monastery. Her fortune was immense, and she donated a large portion of her income to monasteries and churches, particularly supporting the Yuriev Monastery.