We have introduced the Pickering emulsion systems to generate novel confining geometries for the selforganization of monodisperse polymer microspheres using nanoparticle-stabilized emulsion droplets encapsulating the building block particles. Then, through the slow evaporation of emulsion phases by heating, these microspheres were packed into regular polyhedral colloidal clusters covered with nanoparticle-stabilizers made of silica. Furthermore, polymer composite colloidal clusters were burnt out leaving nonspherical hollow micro-particles, in which the configurations of the cluster structure were preserved during calcination. The selfassembled porous architectures in this study will be potentially useful in various applications such as novel building block particles or supporting materials for catalysis or gas adsorption.