An accurate, convenient and inexpensive reductimetric titration method has been developed for the determination of vanadium(V) with iron(II). In this method vanadium(V) is titrated against iron(II)solution in a buffer medium of pH 3.5 – 4.5 [made of sodium acetate and hydrochlaoric acid] and in presence of 0.04M (or above) sodium oxalate. The end-point can be detected potentiometrically or visually using some oxazine dyes (Gallocyanine, Gollamine blue, Celestin blue, and Meladola’s blue) as redox indicators. vanadium(V) in the range of 8-25mg. and 4- 13mg. can be determined by the potentiometric (accuracy + 0.4%) and visual end-point methods (accuracy + 0.6%) respectively. The conditional redox potentials of the oxidant [V(V)/V(IV)] and reductant [Fe(III)/Fe(II)] systems have been measured and based on the potentials data, the conditions needed in the titration has been explained. Based on the SIMUL hyperquade Computer programming, the nature of the species expected to be formed between Fe(III) and oxalate under the optimum conditions has been proposed. The interference of due to other ions has been studied.