In this paper, polystyrene (PS)/SiO2 microspheres were successfully prepared via Pickering emulsion polymerization stabilized solely by ethacryloxypropyltrimethoxysilane (MPTMS) modified SiO2 nanoparticles. The formation mechanisms of PS/SiO2 microspheres with different morphology were investigated under various Pickering emulsion polymerization conditions. The results showed that SiO2 concentrations and initiator sorts would synergistically impact on the morphology of products corresponding to distinct formation mechanisms. When SiO2 concentrations was low and water-solute initiator potassium persulfate (KPS) was used, aqueous nucleation was dominant, which was deduced to the formation of dispersive microspheres sparsely anchored by SiO2 particles. When SiO2 concentrations was increased and oil-solute initiator azobisisobutyronitrile (AIBN) was applied, nucleation in oil phase prevailed which lead to the formation of microspheres densely packed by SiO2 particles. (C) 2012 Elsevier B.V. All rights reserved.