The asymmetric oxidative coupling copolymerization of 6,6'-dihydroxy-2,2'-binaplithalene and dihexyl 6.6'-dihydroxy-2,2'-binaphtlialene-7,7'-dicarboxylate with the copper(I)-diamine catalysts under an O-2 atmosphere was carried out. The copolymerization using the CuCl-(S)-(-)2,2'-isopropylidenebis(4-phenyl-2-oxazoline) catalyst [(S)Phbox], afforded a polymer with the high cross-coupling selectivity of 93%, that is. a copolymer with a mainly alternating structure, in 80% yield. The number-average molecular weight of the methanol-ethylacetate (1/3 v/v)-insoluble part of the copolymer was 1.1 X 10(4). To estimate the enantioselectivity with respect to the cross-coupling linkage in the obtained copolymer, the model asymmetric oxidative cross-coupling reaction with CuCl-(S)Phbox was also examined. and the products showed a 96% cross-coupling selectivity and enantioselectivity of 43% ee (S). (c) 2006 Elsevier Ltd. All rights reserved.