When only a captain he was one of the pro-Russian officers involved in the plot to kidnap Prince Alexander of Battenberg and force his abdication in 1886, for which he was exiled by Prime Minister Stefan Stambolov.

During the First Balkan War (1912–1913), he was in command of the 3rd Army which decisively defeated the Ottoman Empire at Lozengrad and Lule Burgas in Thrace.

At the beginning of spring 1915, Radko Dimitriev commanded the 3rd Army in Galicia facing the Austrians along the line of Gorlice-Tarnów.

Radko Dimitriev claimed correctly that his army had been "bled white" but was removed from command 2 June 1915 and replaced by General Leonid Lesh.

Every piece of his incisive conversation holds together as part of a single and clear view of the whole military position, of which the watchword is 'Forward'."

After he was appointed to fight against the Ottomans in the Caucasus campaign out of favour, he was reappointed in late 1916 to command the 12th army on the Riga front, but in summer 1917 Alexeyev dismissed his commander-in-chief at the front, Ruszky, and the army commander Radko Dimitriev, for weakness and indulgence to the soldiers' committees that had sprung up everywhere after the February Revolution in 1917.