A synthesizing method of hexadecanol / octodecanol-mixed polyoxyethylene ether belongs to the filed of synthesizing technology of organic compounds. Hexadecanol / octodecanol-mixed polyoxyethylene ether is produced through polymerization of raw materials including mixed hexadecanol / octodecanol and ethylene oxide under the existence of a catalyst. The weight proportion of the mixed hexadecanol / octodecanol and ethylene oxide is 1:0.145-18.6; the catalyst is one of or a mixture containing more than one of solid sodium methylate, methanol solution of sodium methylate, KOH, NaOH, etc, and the addition thereof is 0.05-0.2 weight percent of prepared hexadecanol / octodecanol-mixed polyoxyethylene ether. Through rational determination of technological parameters and conditions such as raw material proportion, catalyst amount, polymerization temperature and time, etc., the method of the invention can have the advantages of mild reaction condition, low equipment requirement and high product yield and, in addition, has no impurity or pollutant production. The product has light color, good appearance, wide adjustable molecular weight range and high mutual modulation effect when in mixed application with products having other properties.