Polymeric hybrid precursors, mixtures of polymeric hybrid precursors and polymers, and polymer composite matrices prepared from the mixture of the polymeric hybrid precursors and the polymer. The mixture of the polymeric hybrid precursors and the polymer can undergo a process to form the polymer composite matrix having a cross-linked network of a silasesquioxane based polymer formed from the polymeric hybrid precursors that interpenetrates the polymer. The polymeric hybrid precursors include chemical linkage moieties that are capable of forming non-covalent bonds with portions of the polymer. The polymer composite matrices are useful as biomaterials in medical devices.