In this study, alpha-amylase and glucoamylase were utilized to enzymatically hydrolyze corn starch used to prepare microporous corn starch having varying pore sizes by adjusting the enzymolysis duration. The physicochemical properties, including adsorption capacity, thermal characteristics, and viscosity, of the resulting starches were systematically evaluated, and their application in frozen dough was investigated. The enzymatic hydrolysis significantly enhanced the surface structure, adsorption properties, specific surface area, pore volume, and average pore size of corn starch (p < 0.05), while markedly reducing its viscosity characteristics (p < 0.05). As the enzymatic hydrolysis time increased to 12 h, the gelatinization temperature increased from 75.00 to 83.53 degrees C, and the enthalpy of gelatinization rose from 8.95 to 12.40 J/g, with the crystallinity initially increasing and then decreasing. When microporous starch was incorporated into the frozen dough, the frozen water loss ratio was significantly decreased (p < 0.05), and the transition of strongly bound water to weakly bound water was effectively suppressed. Thus, microporous starches generated after different enzymatic hydrolysis periods exhibited distinct physicochemical characteristics, efficaciously restraining water migration and improving the gluten network structure in frozen dough. These improvements were proportional to the specific surface area of the microporous starch, providing a novel method for enhancing the antifreezing properties of frozen foods.