2-Hydroxy-3-methoxy benzaldehyde thio semicarbazone (2H3MBTS) is proposed as a new photometric reagent for the extractive spectrophotometric determination of V(V) (2H3MBTS) reacts with V (V) and form a stable colored complex in the pH range 6.2 to 7.6. This was well extracted in n-butanol. The absorption spectrum of V (V) and (2H3MBTS) complex in n- butanol shows maximum absorbance at 390 nm. The system obeyed Beer’s law up to 1-8 µg / cm3. The molar extinction coefficient was found to be 18.20×102L mol-1cm-1 and the sensitivity of the method as defined by Sandell’s sensitivity was 0.02797µg cm-2. The Composition of the extracted species was determined by Job’s Continuous variation method, Mole ratio method and slope ratio method and it was found to be 1:2. The proposed reagent is satisfactorily applied for the determination of trace amount of V (V) from synthetic and commercial samples.