A silica-supported chitosan (CS)-palladium complex CS-PdCl2/SiO2 shows good conversion and higher regioselectivity in carbonylation of 6-methoxy-2-vinylnaphthalene. The high selectivity of the catalyst was achieved by the synergic effect of Pd-Ni bimetallic system and by polymer protection. Effects of reaction variables have been studied to optimize the reaction conditions. The hydroesteritication of various substrates were also investigated. XPS and TEM showed that the catalytically active species were composed of particles of nanometric size and then the polymer would serve as a ligand. Finally, the reuse of the catalyst was studied and the mechanism was discussed. (C) 2003 Elsevier B.V. All rights reserved.