A new synthetic procedure of epichlorohydrin was described. Epichlorohydrin was synthesized from alkali and glycerol dichlorohydrin which was synthesized from glycerol and industrial hydrochloric acid in the presence of catalyst and additive. The chief factors affecting on the result of new synthesis were investigated. Suitable conditions were obtained as follow:in the presence of 5# catalyst and additive,the chlorating reaction temperature of glycerol was 115±2℃,the reflux ratio 1∶3,the epoxidation temperature 90℃ and time 15 min. Under the suitable conditions,the overall yield (by glycerol) was 84.6% and the content of product was over 99.5%.