Vanadium is quantitatively retained on 2-(5-bromo-2-pyridyl-azo)-5-diethylaminophenol (5-Br-PADAP)-ammonium tetra-phenylborate with microcrystalline naphthalene or by a column method in the pH range of 2.1-4.5 from a large volume of aqueous solutions of various samples. After filtration, the solid mass consisting of the vanadium complex and naphthalene was dissolved with 5 mL of dimethylformamide and the metal was determined by the third derivative spectrophotometry. Vanadium complex can alternatively be quantitatively adsorbed on ammonium tetraphenylborate-naphthalene adsorbent packed in a column and determined similarly. About 0.05 μg of vanadium can be concentrated in a column from 250 mL of aqueous sample, where its concentration is as low as 0.2 ng/mL. The interference of a large number of anions and cations has been studied and the optimized conditions developed were utilized for the determination of trace amount of vanadium in various samples. Vanadium is quantitatively retained on 2- (5-bromo-2-pyridyl-azo) -5-diethylaminophenol (5-Br-PADAP) -ammonium tetra-phenylborate with microcrystalline naphthalene or by a column method in the pH range of 2.1-4.5 from a large volume of aqueous solutions of various samples. After filtration, the solid mass consisting of the vanadium complex and naphthalene was dissolved with 5 mL of dimethylformamide and the metal was determined by the third derivative spectrophotometry. Vanadium complex can alternatively be quantitatively adsorbed on ammonium tetraphenylborate-naphthalene adsorbent packed in a column and determined analogous. About 0.05 μg of vanadium can concentrated in a column from 250 mL of aqueous sample, where its concentration is as low as 0.2 ng / mL. The interference of a large number of anions and cations has been studied and the optimized conditions developed were utilized for the determination of trace amount of vanadium in various samples.