The application discloses a process method for producing gamma-cyclodextrin by taking ethanol and phenyl-substituted borate as a production aid, and belongs to the technical field of cyclodextrin production. The application uses gamma-cyclodextringlucosyltransferase, takes starch as a substrate, and supplements an ethanol solution of phenyl-substituted borate as a production aid, so that the yield of gamma-cyclodextrin and the proportion of the product are significantly improved. The method is safe and efficient, and can be applied to the production of food and medicine. By using the method, the total conversion rate of gamma-cyclodextrin can reach about 54.14%, and the proportion of gamma-cyclodextrin can be up to 83.07%.