A sensitive and modified method for the separation and estimation of micro amounts of molybdenum(VI) in presence of macro amount of iron(UI) in the thiocyanate system baa been developed. The orange red complex Mo(VI)-SCN in the presence of HCI is quantitatively extractable to an organic phase containing tribeozylamine and chloroform whereas blood red complex Fe(I1I) - SCN remains in the aqueous phase. The Mo-SCN complex baa maximum absorption at 470 run while Fe-SCN complex absorbs at 460 nm. The stability of Mo-SCN complex stands for 72 hours whereas Fe-SCN complex life is for only few hours. The interference due to various ions (cations and anions) baa been also carried out.