Regulating cross-linking of polymers is critical for optimizing the physical properties of polymer networks. Herein, we present a strategic approach for designing polymer networks using dithiol-functionalized metal-organic frameworks (MOFs) with both one- and three-dimensional pore architectures. Upon thermal treatment, thiyl radicals were generated from the MOFs through the dissociation of S-H bonds, as confirmed by electron spin resonance measurements. Unlike in solution and bulk phases, the confinement of these radicals within the MOFs effectively suppressed homocoupling reactions, thus enabling their function as densely packed cross-linkers. The thiol-ene reaction between the MOFs and