The pressure oxidation of molybdenite concentrates in acidic and alkaline media has been studied. The conditions of the selective oxidation of copper and iron sulphide minerals with a quantitative copper leaching by ferrous-ferric-sulphate solution have been found and explained from the point of view of electrochemical kinetics. The partly oxidised residue consisting of molybdenite and (hydro-) oxide of iron (III) was then decomposed by oxygen in alkaline media. Effects of the main parameters, such us oxygen pressure, leaching temperature, solid-liquid phase ratio, autoclave stirring speed as well as lixiviants nature on the molybdenite oxidation rate have been established.