This paper discussed the Oscilloscopic polarography for the determination of tungsten, molybdenum in geochemical exploration samples from the ore smelting method, system of acidity, test temperature, concentration of each reagent in base solution, reactive time of balance, the interference and elimination of coexisting substances, and provided the optimized conditions. Determination of sensitivity is greatly improved by this method, and the method has high efficiency, low cost, good repeatability, the measuring results are accurate and reliable.