A novel process was approached to prepare a series of silica polymer hybrid microspheres prepared from water-in-oil (W/O) suspension containing a suspension of polymer with reactive sites and silica nanoparticles (SiPs) of varying size as aqueous phase. Heating promoted the solidification of the particles. Inorganic microspheres were obtained by simply burning off the organic parts of the hybrid mesoporous microspheres and porosity increases hierarchically from mesoporous to macroporous with the increase of size of SiPs.