A recyclable catalytic system has been developed that comprises an inorganic polymer matrix consisting of non-functionalized silica, which encapsulates copper by direct interaction with the matrix. Cu is fixed to a silica support of nanometric dimensions by physical entrapment within a silica sol-gel matrix. Samples with different Cu loadings were studied in order to maximize and optimize the amount of entrapped Cu within the silica matrix. This entrapment limits the diffusion of the metal to the solution, thus ensuring negligible contamination of the product by the metal while simultaneously providing a stabilizing environment. This robust and versatile heterogeneous catalyst was evaluated in Huisgen and Ullmann intramolecular coupling reactions. (C) 2015 Elsevier B.V. All rights reserved.