Horseradish-peroxidase (HRP)-catalyzed polymerization of 1,5-dihydroxynaphthalene (1,5-DHN) gave poly(1,5-DHN), P(1,5-DHN), constituted of the 1,5-dihydroxynaphthylene unit, unit A, the 1(or 5)-hydroxy-5(or 1)-oxynaphthylene unit, unit B, and 1,5-dioxynaphthalene unit, unit C. HRP-catalyzed polymerization of 2,6-DHN proceeded selectively at the aromatic ring to provide P(2,6-DHN) constituted of only the 2,6-dihydroxynaphthylene unit. Acetylated polymers, P(1,5-DHN)-Ac and P(2,6-DHN)-Ac, were obtained by reactions of P(1,5-DHN) and P(2,6-DHN) with acetic acid anhydride. Reaction of P(1,5-DHN) with Al(Et)q'(2) (q' = 2-methyl-8-quinolinolato) caused Al-O bond formation to give a photoluminescent polymer-aluminum complex, P(1,5-DHN)-Alq'(2). Optical, electrochemical, and thermal properties of P(1,5-DHN), P(2,6-DHN), and P(1,5-DHN)-Alq'(2) were investigated. (C) 2004 Elsevier B.V. All rights reserved.