A novel thermally stable and low dielectric poly(2-naphthol) containing an adamantyl unit (3) has been developed. Polymer 3 was easily prepared by oxidative coupling polymerization of (1,3-adamantyl)bis(2-naphthol) with CuCl(OH)TMEDA as a catalyst. The polymerization produced regiocontrolled polymer 3 with a number-average molecular weight of 10,500 Da and a molecular weight distribution of 4.1. The 5% weight loss temperature of polymer 3 was 480 degrees C and no glass transition temperature was observed. The dielectric constants (E) of polymer 3 estimated from the refractive index and the capacitance were 2.92 and 2.96, respectively. (c) 2006 Elsevier Ltd. All rights reserved.