The asymmetric oxidative coupling polymerization of methyl 6,6'-dihydroxy-2,2'-binaphthalene-7-carboxylate with the copper-diamine catalysts under an O-2 atmosphere was carried out. As is the case with the CuCl-2,2'-(S)-isopropylidenbis(4-phenyl-2-oxazoline) [(S)IPhO] catalyst, a polymer with a high cross-coupling selectivity of 96% was obtained in 71% yield, whose THF-soluble part had a number-average molecular weight of 4.5 x 10(3). To estimate the enantioselectivity with respect to the cross-coupling linkage in the obtained polymer, the model asymmetric oxidative cross-coupling reaction with CuCl-(S)IPhO was also conducted, and the products showed a 94% cross-coupling selectivity and enantioselectivity of 31% ee (S). (c) 2005 Wiley Periodicals, Inc.