Molybdenum(V) has been found to react with thiocyanate and N1-hydroxy-N1,N2-diphenylbenzamidine (HDPBA) to form a 1:3:1(Mo:SCN−:HDPBA) complex with a molar absorptivity of 13100 M−1cm−1at 470 nm. The complex is quantitatively extractable into 2.5% (v/v) amyl alcohol in benzene from 4–6 M hydrochloric acid solutions and the system obeyed Beer's law in the concentration range of 0.5–9.6 μg mL−1of Mo. Optimum conditions for the extraction and determination of molybdenum have been established and a precise, sensitive and highly selective method has been developed for the determination of molybdenum(V) by solvent extraction and spectrophotometry. The method has been successfully applied to the determination of molybdenum in standard steels and synthetic matrices.