A novel way to prepare polymer hair/polysilsesquioxane core hybrid nanospheres is presented based on a self-assembly and gelation process of a reactive block copolymer, poly(ehtyelen oxide)-block-poly[3-(trimethoxysilyl)propyl methacrylate] (PEO113-b-PTMSPMA(206)). Nanospheres of uniform size were obtained. Transmission electron microscopy (TEM), dynamic light scattering (DLS), and static light scattering (SLS) were employed to characterize the products.