Zinc chloride was immobilized onto chloroacetylated polystyrene via different linkages to afford Polymer-supported Lewis acid catalysts. The functionalized beads and the immobilized catalysts were characterized by elemental analysis, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and inductively coupled plasma and thermal analysis. The reaction of aldehydes with anhydride in the presence of the supported catalysts was investigated. The effects of various parameters, including the solvent, amount of catalyst, and temperature, on the reaction were also studied. We found that the reaction proceeded smoothly under solvent-free conditions at room temperature and afforded the corresponding acylals in good yields. Moreover, the catalysts could be recovered easily and reused several times without a significant loss in activity. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 112: 2087-2093, 2009