Photoresponsive materials that change in response to light have been studied for ar ange of applications.T hese materials are often metastable during irradiation, returning to their pre-irradiated state after removal of the light source. Herein, we report ap olymer gel comprising poly(ethylene glycol) star polymers linked by Cu 24 L 24 metal-organic cages/ polyhedra (MOCs) with coumarin ligands.I nt he presence of UV light, ap hotosensitizer,a nd ah ydrogen donor,t his "polyMOC" material can be reversibly switched between Cu II , Cu I ,and Cu 0 .The instability of the MOC junctions in the Cu I and Cu 0 states leads to network disassembly,forming Cu I /Cu 0 solutions,respectively,that are stable until re-oxidation to Cu II and supramolecular gelation. This reversible disassembly of the polyMOC network can occur in the presence of af ixed covalent second network generated in situ by copper-catalyzed azide-alkyne cycloaddition (CuAAC), providing interpenetrating supramolecular and covalent networks.