The invention discloses a preparation method of zinc sulfide nuclear hollow microspheres. The preparation method is characterized by comprising the following steps: (1) dosing: dissolving a phenylamine monomer in an organic solvent insoluble in water to obtain a solution A for use; sequentially dissolving a zinc-containing compound, strong base and a sulfur-containing compound in deionized water to obtain a solution B; adding the prepared persulfate aqueous solution into the solution B to obtain a solution C; and finally, adding the solution C into the solution A to obtain a insoluble two-phase mixed solution with a clear interface; (2) standing at constant temperature and reacting for 12-24 at room temperature, wherein slight yellow precipitate appears on the two-phase interface; (3) washing; and (4) drying to obtain the ZnS nuclear hollow microspheres. The method is simple and easy to implement, and the morphological control over the synthetic material is stable. The obtained product can be applied to the fields such as secondary battery materials, photovoltaic devices, photocatalysts and gas sensors.