The invention discloses a phase transfer catalytic synthesis method of 3, 4-epoxy cyclohexyl methyl-3', 4'-epoxy cyclohexyl formate. The method comprises the following steps of: carrying out Tischenko reaction on 3-cyclohexene-1-formaldehyde as a raw material to obtain an epoxidized raw material 3, 4-cyclohexene formic acid-3', 4'-cyclohexene methyl ester, and performing epoxidation on double bonds of the 3, 4-cyclohexene formic acid-3', 4'-cyclohexene methyl ester by taking hydrogen peroxide as a green oxygen source under the catalysis of a phase transfer catalyst peroxy phosphotungstic acid (peroxy phosphomolybdic acid) quaternary ammonium salt, thereby obtaining cationic epoxy resin 3, 4-epoxy cyclohexyl methyl-3', 4'-epoxy cyclohexyl formate for 3D printing. According to the preparation method, the peroxy phosphotungstic acid (peroxy phosphomolybdic acid) quaternary ammonium salt phase transfer catalyst is applied, a buffer agent inhibits hydrolysis of the product, so that high yield is achieved, efficient recovery of the catalyst is achieved, and the prepared product has the advantages of being resistant to weather, high in purity, colorless, resistant to yellowing, good in electric insulativity and low in viscosity and has good application values in the fields of 3D printing, coatings, packaging, electronics, automobiles and the like.