By adding polystyrene homopolymer in the solid state, superlattice structures of poly (4-vinyl pyridine) core-polystyrene shell type polymer microspheres were hierarchically changed from a disordered state to a face-centered cubic via a body-centered cubic. The transition of the lattice structures was investigated from the view point of the excluded volume of the microsphere, which was controlled by a changing of the molecular weights and blend tarios of polystyrene homopolymers.