Regiocontrolled polymer (2) having 2-naphthol unit was prepared by oxidative coupling polymerization of bis(2-naphthol) (1). Polymerizations were conducted in dichloromethane in the presence of [di-mu-hydroxo-bis(N,N,N',N' -tetramethylethylenediamine)copper(II)] chloride [CuCl(OH)TMEDA] under air at room temperature, producing polymers with number-average molecular weights up to 12,000. The structure of polymer 2 was characterized by 270 MHz H-1-NMR and 68.5 MHz C-13-NMR spectroscopies and was estimated to consist almost completely of 1,1'-linkage. The polymer was readily soluble in polar aprotic solvents and tetrahydrofuran at room temperature. Thermogravimetric analysis of polymer 2 showed 10% weight loss at 450 degrees C in nitrogen. The model reactions were studied to clarify the applicability of CuCl(OH)TMEDA for coupling of naphthol derivatives.