A simple spectrophotometric method was optimized for the speciation vanadium using pyrocatechol violet as chelating agent. Vanadium(V) was determined by pyrocatechol violet at pH 3.0, whereas vanadium(IV) was simultaneously determined using same procedure after oxidation of vanadium(IV) by potassium permanganate. The linear range for vanadium(V) is 0.2-4.0 μg/mL with a detection limit of 0.038 μg/mL. The proposed spectrophotometric method was found selective for vanadium(V) with high tolerence limit of foreign ions. The proposed method was validated by standard addition method at different levels of both understudied species with >92 % recoveries in water, black pepper and coal samples.