A highly sensitive, selective, and rapid method for the spectrophotometry determination of vanadium(V) at trace levels is described. The method is based on the selective extraction of vanadium(v) from strongly acidic (3–6 M hydrochloric acid) met ium with solution of N-0-methoxyphenyl-2- thenohydroxamic acid (0MTHA) in chloroform. The extract is then equilibrated with 3-(0-carboxyohenyl)-1-phenyltriazine-N-oxide(CPPTNO) at pH ≃ 1.5 and the resulting colour is measured at 445 nm. The colour system obeys Beer's law over the range 0–20 -μg/ml of vanadium; the molar absorptivityat the wavelength of maximum absorption (445 nm), and the Sandell sensitivity of the method are 1.1 × 1041. mole−1cm−1and 0.005 μg/ml respectively.