Summary: 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(ethylene oxide)‐block‐poly[3‐(trimethoxysilyl)propyl methacrylate] (PEO113‐b‐PTMSPMA206). 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.