A catalyst containing aluminum chloride supported on a mesoporous aromatic framework (PAF) was synthesized. The effect of the PAF-AlCl3 catalyst on the products of the hydrogenation-hydrocracking of naphthalene in the presence of PAF-NiMoS and PAF-NiWS bimetallic catalysts was studied. The addition of PAF-AlCl3 markedly enhances the yield of reaction products and the best naphthalene conversion results were obtained by adding sulfur to the reaction mixture. Thus, naphthalene can be hydroconverted quantitatively to reaction products, 70% of which are the result of hydrogenation and 30% the result of cracking, using the PAF-NiMoS/PAF-AlCl3 (1:3.3 wt. ratio) catalyst system.