Hydrolysis and polycondensation of the coupling agent (aminopropyl)triethoxysilane (APS), axially coordinated to the redox-active complex [Rh-2(form)(2)(CH3COO)(2)(APS)(2)], lead to the insertion of redox-active inorganic microdomains into a siloxane network; the new polymers undergo cyclic redox reactions indicating that dirhodium(II,II) centres retain their redox activity even when incorporated into siloxane networks.