A sensitive and modified method for the extraction and determination of the Mo(V) in the thiocyanate system has been developed. The orange red complex formed between Mo(V) and SCN is quantitatively extractable from an aqueous phase into an organic phase containing isobutyl alcohol. The complex gave maximum absorption at 470 nm and the system Obeys Beer's law in the range 0.01-7.0 ppm of molybdenum in the solution. The colour is stable for 24 hours and the molar absorptivity at 470 nm is 1.51 x 10(4)l mole-1 cm-1. The extractability of the complex by the tertiary alcohol suggests that the coloured species is anionic. Most of the common cations and anions do not interfere. The method developed was successfully applied to the analysis of molybdenite ores from Kohistan.