Chloroperoxidase was encapsulated into hybrid polysaccharide-silica matrices by means of sol-gel processing. Chitosan was found to be the most effective additive to improve enzyme catalytic performances. At the standard initial experimental conditions, enzyme was able to perform five complete reaction cycles and a substrate conversion of 60% at the sixth cycle. The optimization of the procedure, which consisted in the reduction of reaction time, the elimination of washes between cycles and the increase of the chitosan concentration in matrices, allowed a considerably higher reusability of the biocatalyst, up to 18 consecutive reaction cycles. Moreover, immobilized enzyme displayed an excellent thermal stability and even at 70 degrees C its activity remained higher than 95% also after 2 h of incubation. These results paved the way to the application of chloroperoxidase for academic synthesis and industrial production of chemicals. (C) 2014 Elsevier B.V. All rights reserved.