With n-butanol/CTAB/cyclohexane as micro emulsion system, sodium tungstate and hydrochloric acid as raw material, alkali metals (Na+, K+) nitrate as dopant, pure WO3、Na+-WO3, K+-WO3 and Na+/K+-WO3 powders were prepared by ultrasonic micro-emulsion method; And performances of samples were analyzed by visible spectrophotometer. Photocatalytic activity study show that alkali metal sodium ion and potassium ion doped, photocatalytic activities of WO3 are improved markedly; When doping amount is 1.0%, catalyst amount is 2g/L, methyl orange concentration is 20mg/L, degradation time is 80 min, Na+-WO3 powder has the best photocatalytic degradation performance at 460nm, and the degradation rate is as high as 65%.