The invention relates to a synthesis process of air-drying epoxy vinyl ester resin, which consists of bisphenol A type epoxy resin with low epoxy equivalent and high epoxy equivalent, and organic monobasic unsaturated carboxylic acid with a catalyst at 120-160 ° C. React in the presence of a polymerization inhibitor, and then be diluted with a cross-linkable monomer to synthesize. The resin has good air-drying property, surface dry ≤ 0.5 hours, solid dry ≤ 4 hours, moderate viscosity, good wettability with glass fiber and glass felt, excellent physical and mechanical properties, excellent chemical corrosion resistance, suitable for such as hand lay-up, winding, stretching Extrusion, injection and other FRP molding processes. In the synthesis process of the invention, the production process is simplified, the production energy consumption is reduced, and the product has good stability.