In this paper, we adopt a facile method to prepare vinyl functionalized hollow silica spheres. Vinyl functionalized silica shells were coated on positively charged polystyrene particles by hydrolysis and condensation of vinyltriethoxysilane (VTES), the polystyrene cores were dissolved subsequently in the same medium to form monodispersed vinyl functionalized hollow silica spheres. Neither additional dissolving nor a calcination process is necessary to remove the polystyrene cores. Transmission electron microscopy (TEM), FT-IR analysis, TGA and porosity measurements were used to characterize the monodispersed vinyl functionalized hollow silica spheres.