It was studied complexation of vanadium (V) with a reagent synthesized on based pyrogallol-2,3,4-trihydroxy-5-sulphoazonaphtalin by spectrophotometric method. It was found that at pH 5, λmax = 437 nm formed intensively colored binary complex. It was also studied the influence of the third components on complexation. As the third component we used setylpyridine chloride, setylpyridine bromide and decamethoxin. Optimal conditions was established of complexation. It is found that the maximum exit of mixed ligand complexes was observed at pH 3, λ=471, 479 and 466 nm, respectively. It was calculated stability constants of complexes, the ratio of reacting components in the composition and concentration ranges submission to Beer's law. It was studied the influence of foreign ions and masking substances on the complexation. The developed method was approbated in the photometric determination of vanadium(V) in the clay samples.