Mononuclear unsymmetrical N-heterocyclic carbene-gold complexes and the corresponding solid catalysts in which a gold-carbene complex has been immobilized on silica gel, ordered mesoporous silica (MCM-41), and delaminated zeolite (ITQ-2) have been prepared. These new catalysts have been tested in the hydrogenation of alkenes and the Suzuki cross-coupling reaction to afford selectively non-symmetrical biaryls. These reactions were studied with the soluble as well as with the heterogenized counterpart catalysts. The high accessibility introduced by the structure of the supports allows the preparation of highly efficient immobilized catalysts with TOFs up to 400 h−1. Moreover, the heterogenized complexes were reused and no deactivation of the catalysts can be observed.