Popović was born in 1881 in Sjenica, Kosovo Vilayet, Ottoman Empire (present-day southwestern Serbia). His family fled from Ottoman rule and settled in Kragujevac, where he attended school. After graduating from the Military Academy in Belgrade in 1903 with the rank of infantry second lieutenant, Vojin Popović chose to join the chetnik organisation in 1905, and in 1911 joined the secret organization "Unification or Death" (Black Hand). He fought against the Ottomans in Macedonia and Old Serbia between 1905 and 1912 (battles at Čelopek, Кumanovo, Prilep, Bitola, and the bank of the Vardar) and against the Bulgarians on the river Bregalnica in 1913. He won military renown in the First World War battles of the Drina, the Коlubara and particularly for Cer, and was decorated with the Order of the Кarađorđe Star, 4th and 3rd class (officer and commander). He was promoted to the rank of infantry lieutenant colonel of the Serbian Army, and despite his reputation of being a strict and unbendable officer, he was favoured with complete trust. He was remembered above all as the most exemplary chetnik leader (vojvoda) because of his exceptionally courageous and inspirational military leadership. His units provided security for Crown Prince Aleksandar Karađorđević during the withdrawal across Аlbania which ensued after the heavy losses Serbia suffered in 1915. In the winter of 1916 he commanded the volunteer detachment engaged in battle with Bulgarians over the strategic peak of Mt Nidža, Kajmakčalan, on the Salonika Front. He was wounded at Grunište vis in the River Crna area, but continued to pursue the enemy. On 29 November 1916, at the final stage of the battle, he died of a bullet to the heart.