We have introduced a strategy to modulate supramolecular polymer network properties through the incorporation of cross-links containing two distinct supramolecular interactions-metal-ligand coordination and host-guest binding. This configuration was shown to enable unique bulk functions, specifically of polyMOC gels, that have not been reported and may be inaccessible for traditional supramolecular networks where such interactions are incorporated independently. The introduction of guest molecules to these materials enabled tuning gel relaxation time by over an order of magnitude while maintaining constant stiffness. Further, the introduction and modulation of guest binding strength was shown to enhance the stability of polyMOC gels in the presence of super-stoichiometric Pd 2+ and competing pyridine-containing ligands, illustrating the synergistic stabilization property of two interactions in parallel within a single network junction. Selective sol-gel transitions gated by guest binding strength could also be realized by simply adjusting the amount of excess Pd 2+ in the system. Finally, selective guest binding was observed to drive MOC self-sorting, which could be leveraged to enable up to six sequential sol-gel transitions in a single polyMOC gel material composed of a mixture of polymer-bound and small-molecule ligands. A general theoretical description of this phenomena was presented, which will aid in the extension of these properties to other variations of polyMOC gels or other materials with nested supramolecular interactions. Altogether, these results expand the functionality and stimuliresponsive properties achievable within supramolecular polymer networks through the judicious design of network junction chemistry and structure. In the future, the nested supramolecular junction concept introduced here may leverage the vast existing body of known MOC host-guest binding properties to accelerate the creation of soft materials with exquisitely selective smallmolecule-driven property changes for applications ranging from sensing to biomaterials.