Highly sensitive and selective direct spectrophotometric method is proposed for the determination of aluminium in various real samples. 5- methoxy-2-[[[4-methoxy-3, 5-dimethyl-2-pyridinyl] methyl] sulfinyl]-1HBenzimidazole reacts with V(V) forming greenish yellow coloured soluble complex in aqueous dimethyl formamide which has a λmax at 410 nm in the pH range 4.0-7.0. The system obeyed Beer’s law in the range 0.508 – 0.854 μg mL-1 of V (V). The molar absorptivity is 2.65 x 104 L mol-1 cm-1 and The Sandell’s sensitivity is 0.0825 μg/cm2. The standard deviation of the method for ten determinations of 0.579 μg/ml of V (V) is 0.0086. The correlation coefficient (γ) of the calibration equation of the experimental data is 0.9897. Studies on effect of diverse ions showed almost all the anions a majority of the cations do not interfere in more than 30 fold excess. The direct method was applied for the determination of vanadium biological samples like cabbage leaves and Goat leaves, blood and urine samples Tap water and plant materials.