SiO₂ coated by ZnS nanocrystalline three-dimensional core-shell or hollow nanospheres can be used as building blocks for photonic crystals. To produce these particular three-dimensional nano-materials, a layer-by-layer self-assembled method was used. The electrostatic on the surface of nanometer SiO₂ templates could absorb ZnS nanocrystal and form a layer of thickness-controlled shell. The hollow nanospheres were produced by 5％ hydrofluoric acid etched the SiO₂ templates. The core-shell structure and hollow nanospheres were verified by XRD, UV, PL, TEM, SEM and AFM. The results indicate that after the SiO₂ is coated by ZnS nanocrystalline, the core-shell surface is close and neat, and the particle size is homogeneous. The configuration of ZnS hollow nanospheres is intact, and the thickness is well-distributed.