Through the Ruthenian National Association, Dmytriw travelled to Canada in April 1897 to serve the spiritual needs of the Ukrainian Canadian settlers. Able to speak Ukrainian, German and English he became an interpreter for Canadian immigration. In Canadian history, Dmytriw's most notable contribution is in writing about the history and tribulations of early Ukrainian settlers.
Dmytriw was only in Canada until August 1898, but as the first Ukrainian priest in Canada he organized the first Ukrainian parishes in Terebowla, Manitoba, Stuartburn, Manitoba and Edna, Alberta and was an advocate of the a separate Ukrainian Catholic church in Canada. This was initially opposed by the Canadian Catholic hierarchy, especially Archbishop Adélard Langevin, but came to fruition with the appointment of Nykyta Budka as apostolic exarch for Ukrainian Canadian Catholics.