Hydrofluoric acid has been used as a novel stripping agent for molybdenum(VI) after its extraction with Cyanex 301. In the extraction step, the effects of parameters such as type and initial concentration of acid, type of diluent, extractant concentration, metal concentration and temperature have been studied. In the stripping step, the effects of various stripping agents on stripping efficiency have been investigated. Hydrofluoric acid has been chosen as an effective stripping agent, and the effects of concentration of hydrofluoric acid, stripping time, volume of hydrofluoric acid and the number of stages of stripping have been studied. Molybdenum(VI) has been effectively separated from a large number of elements in binary mixtures, with a very high tolerance limit. Finally, the optimized method has been extended for the analysis of Mo(VI) in spent molybdenum catalysts.