Abstract:A method for the determination of Vanadium in Vanadium-Aluminium master alloys by KMnO4 -Ferrous titration method is presented .The sample was digested by H2SO4-H3PO4-HNO3. The influence of the method for sample digestion; the amount of KMnO4 and NaNO2; the interference of co-existence elements were discussed so as to confirm the best condition. The proposed method was applied to determine the Vanadium contents in six Vanadium-Aluminium master alloy samples whose Vanadium content was different from 49.45% to 83.33%. The results showed that the relative standard deviations(n=11) were all about 0.2%, and the recoveries were in the range of 98.2%~102.5%.Compared with 7 different laboratories , the results were consistent without significant deviation. This method has the advantages of fast，accurate and a wide analytical range. It is suitable for determination Vanadium in Vanadium-Aluminium master alloys.