Crosslinkable composite microspheres were prepared by heterocoagulation of epoxy resin nanoparticles onto polystyrene microspheres. The corresponding hollow microspheres were created after removal of the core. The surface morphology was tunable from smooth to rough by controlling the degree of crosslinking of the shell nanoparticles. A positively charged polyelectrolyte could be easily adsorbed onto the composite microspheres to facilitate further synthesis, e.g., layer-by-layer deposition and a sol-gel process to form inorganic materials.