The asymmetric cyclocopolymerization of bis(4-vinylbezoate) of a chiral diol with styrene is a promising method for the preparation of optically active polystyrene derivatives because of main-chain chirality. However, the mechanism for chirality induction from the chiral diol to the main chain is still unknown. To clarify the chirality induction mechanism, we carried out the radical cyclizations of (2S,3S)-2,3-butanediyl bis(4-vinylbenzoate), (2S,4S)-2,4-pentanediyl bis(4-vinylbenzoate), and (2S,5S)-2,5-hexanediyl bis(4-vinylbenzoate) with tri-n-butyltin hydride or allyltri-n-butyltin as a chain-transfer reagent as model reactions for asymmetric cyclocopolymerization. The absolute configuration was determined with single-crystal X-ray crystallography and a circular dichroism exciton chirality method. The distribution of the stereoisomer showed (R)-configuration selectivity (21-34% diastereomeric excess) in the intramolecular cyclization and an extremely low extent (<1%) of the (S,S)-cyclized product among the four stereoisomers. Therefore, chirality induction is caused by the selective inhibition of the (SS)-racemo configuration. (C) 2004 Wiley Periodicals, Inc.