The oxidative coupling polymerization of triphenylamine derivatives having 2-naphthol moieties with a CuCl-2,2'-isopropylidenebis(4-phenyl-2-oxazoline) catalyst under an O-2 atmosphere was carried out. The polymerization of the monomer bearing both the hydroxynaphthoate and naphthol units afforded a hyperbranched polymer with a high cross-coupling selectivity of > 99%, which showed a number-average molecular weight of 20.3 x 10(3). In addition, the obtained polymer was quite soluble in THE The photoluminescence and electrochemical properties of the obtained polymers were also examined. (C) 2007 Wiley Periodicals, Inc.