"Dmitrii Donskoi" was assigned to the cruiser force of the Second Pacific Squadron and departed Libau on 15 October 1904 bound for Vladivostok with Captain 1st Rank Lebedev in command. En route in the North Sea, she was damaged by friendly fire from seven sister ships in mistake for a Japanese vessel during the Dogger Bank Incident of 21/22 October. The ship passed the Cape of Good Hope on 20 December. Whilst approaching the Strait of Tsushima on 27 May 1905, the Russian force was intercepted by the Japanese in the Battle of Tsushima. The cruiser was assigned to defend the transport ships at the rear of the Russian formation and was not seriously engaged during the day.