The multilayer core/shell polymer microspheres with high carboxyl content were prepared by seed emulsion polymerization,then treated with ammonia to form monodisperse polymer hollow microspheres. The functional groups of the core/shell microspheres were characterized by FTIR, and the structure of the hydrophilic core/hydrophobic shell was confirmed by the conductometric titration curve and the Zeta potential analyze. The effects of the content of sodium dodecyl sulfate(SDS) and the mole ratio of alkali to acid in the process of alkali treatment on the size and morphology of microspheres were studied. Results show that the diameter of core, multilayer core/shell and hollow microspheres as well as the hollow size decrease with the increasing of SDS content. Enhancing the mole ratio of alkali to acid is favorable to the volume expansion of microspheres and leads to the increasing of both the diameter of hollow microspheres and the hollow size inside. Furthermore, the polymer hollow microspheres with the diameter of 355～790 nm and hollow size of 118～450 nm could be obtained by varying SDS mass from 0.01 g to 0.03 g and the mole ratio of alkali to acid from 1.0 to 2.0.