A rapid and reliable method for the spectrophotometric determination of the established analytical reagent N-o-tolylbenzohydroxamic acid (o TBHA) with vanadium (V) has been developed. The chloroform extractable violet complex formed byo-TBHA with vanadium(V) in hydrochloric acid (>2M) media, showing a broad absorption band at 520 nm, is utilized for this purpose. The molar absorptivity of the extracted complex in terms ofo-TBHA is 2500 ±1001. mole−1 cm−1. The effects of several experimental variables such as the time of shaking of the phases, volume and temperature of aqueous phase, mole ratio ofo-TBHA to vanadium(V) and concentration of mineral acids on the determination ofo-TBHA have been investigated.o-TBHA has been determined in the presence of several classes of organic compounds such as amides, esters, anhydrides, etc. The new method is successfully applied for the determination of distribution ratios ofo-TBHA between different organic solvents and water and solubilities in different solvents.