A very simple and rapid method for the extractive separation and photometric determination of vanadium is worked out using benzoylacetone as a complexing reagent for V(III), produced on reduction of V(V) with sodium dithionite in dil acetic acid medium. The colored complex is extractable into benzene. The interfering effect of a large number of elements is eliminated completely leading directly to the determination of the metal ion present in traces in samples. The method is applicable to the analysis of different technical samples and the results obtained are highly reproducible. Metal to ligand ratio in the extracted species is determined as 1 : 3.