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In 1834, Father John was transferred to Sitka Island, to the town of Novoarkhangelsk, later called Sitka. He devoted himself the Tlingit people and studied their language and customs. His studies there produced the scholarly works ''Notes on the Kolushchan and Kodiak Tongues'' and ''Other Dialects of the Russo-American Territories, with a Russian-Kolushchan Glossary''.

In 1838, Father John journeyed to St. Petersburg and Moscow, Russia, and Kiev, Ukraine, to report on his activities and request an expansion of the Church's activities in Russian America. While he was there, he received notice that his wife had died. He requested permission to return to Sitka. Instead, it was suggested that he take vows as a monk. Father John at first ignored these suggestions, but, on [[November 29]], 1840, made his vows. He chose the name ''Innocent'' in honor of Bishop Innocent of Irkutsk.

On [[December 15]], 1840, [[Archimandrite]] Innocent Veniaminov was consecrated Bishop of Kamchatka and Kuril Islands in Russia and the Aleutian Islands in Russian America. His see was located in Novoarkhangelsk, which he returned to in September 1841. He spent the next nine years in the administration of his see as well as on several long missionary journeys to its remote areas. On [[April 21]], 1850, Bishop lnnocent was elevated to Archbishop. In 1852, the Yakut area was admitted to the Kamchatka Diocese, and in September 1853, Archbishop Innocent took up permanent residence in the town of Yakutsk. Innocent took frequent trips throughout his enlarged diocese. He devoted much energy to the translation of the scriptures and service books into the Yakut (Sakha) language.

In April 1865, Archbishop Innocent was appointed a member of the Holy Governing Synod of the Church.