The invention belongs to the technical field of ion exchange resin, and relates to application of a composite initiating agent in preparation of the ion exchange resin. The application includes the steps of (1) adding industrial salt in a recycled NaCl liquid, stirring to dissolve, adjusting specific gravity, adding hydroxyethyl cellulose, and heating with stirring to obtain a water phase; (2) weighing and mixing acrylonitrile, methyl acrylate and triallyl isocyanurate, adding a mixed solution of the composite initiating agent and divinylbenzene, and adding methylbenzene with stirring to obtain an oil phase; (3) mixing the water phase with the oil phase, heating to react, transferring into an oil blowing kettle to filter off the liquid, adding hot water to immerse a ball body, stirring, heating to a certain temperature by vapor, reacting under the condition that pressure in the oil blowing kettle is controlled, and screening through a hot air drying screen to obtain polymerized white beads. By adopting the composite initiating agent, in a production and operation process, reactions are performed in stages, processes are enabled to be stable in reaction, operations are easy to control, and an obtained product is excellent in performance, safe and environment-friendly.