Poly(dinaphthylene ether)s (4) were prepared by oxovanadium-catalyzed oxidative coupling polymerizations of di(1-naphthoxy) compounds (3). Polymerizations were conducted in nitrobenzene in the presence of vanadyl acetylacetonate, trifluoromethane sulfonic acid and trifluoroacetic anhydride under an oxygen atmosphere at room temperature and produced poly[1,5-di(1-naphthoxy) pentane] (4a) having weight-average molecular weights up to 50,000. Vanadyl acetylacetonate acted as an oxidant and the polymerization was conducted using only 5% vanadyl acetylacetonate based on the monomer. The structure of polymer 4a was characterized by C-13-NMR spectroscopy, and selective coupling was found to occur at the C-4 position of the 1-substituted naphthalene ring due to the high electron density at this carbon.