Radical cyclocopolymerization of the dimethacrylate 1 (M(1)), which was derived from 1,2:5,6-di-O-isopropylidene-D-mannitol, with styrene (M(2)) induced new chirality in the polymer chain. The removal of the chiral template in the copolymer 2 followed by treatment with diazomethane gave optically active poly(methyl methacrylate-co-styrene) (4). Polymer 4 had more active chirality upon increasing the M(1) unit, thus indicating that the new chirality should be induced by the M(1) diad unit rather than the isolated M(1) unit. Characteristics of monomer 1 include the considerably higher fraction of tactic triad rr in poly(methyl methacrylate) (PMMA) derived from the homopolymerization and the larger probability of forming the raceme diad of the M(1) unit during the intermolecular reaction of the copolymerization. In polymer 4, the origin of chirality was assigned to the chiral tetrad sequences of the MMA unit which were induced by participation of the raceme configuration.