The quaternary ammonium salt Aliquat 336 (A336; R4N+Cl-) and the azo dye 4-(2-thiazolylazo)orcinol (ТАО) were examined as constituents of a water-isobutanol extraction-chromogenic system for vanadium(V). Under the optimum conditions (cTAO = 1.6´10-3 mol dm-3, cA336 = 1.3´10-2 mol dm-3 and pH 5.0), vanadium(V) is extracted as a ternary complex which can be represented by the formula (R4N+)[VO2(TAO2-)]. The key extraction-spectrophotometric characteristics were determined. The interfering effect of foreign ions was studied as well. The wavelength of maximum absorption (λmax), molar absorptivity (εmax), constant of extraction (Kex) and fraction extracted (E) were found to be λ = 547 nm, ε = 3.1×104 dm3 mol-1 cm-1, Log Kex = 2.8 and E = 90.2%, respectively. Beer's law was obeyed in the range of 0.084-2.0 mg cm-3 and the limit of detection was 25 ng cm-3 of vanadium(V).