Summary: Hydrolysis and polycondensation of the coupling agent (aminopropyl)triethoxysilane (APS), axially coordinated to the redox‐active complex [Rh2(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.