Poly (4-vinylpyridine) (P4VP) core-policy (alpha-methylstyrene) shell polymer microspheres have been synthesized by cross-linking the P4VP spherical microdomains of poly (alpha-methylstyrene-b-4-vinyl-pyridine) diblock copolymer films with 1,4-dibromobutane. These microspheres formed a lattice with a body-centred cubic structure near the overlap concentration. In the bulk of as-cast film of microspheres, this structure changed to a face-centred cubic lattice. After these microspheres formed a cubic lattice in methyl methacrylate (MMA) monomer, the polymeric superstructures were constructed by locking permanently ordered lattice in a solid matrix by means of free radical polymerization of MMA monomer. This technique is one of the best methods for creating nanoscopic polymeric superstructures composed of three phase separated microdomains. (C) 1997 Elsevier Science Ltd.