Polymer gels are often very soft due to their low branch functionality (f) and the inevitable presence of defects (e.g., primary loops or dangling chains). Polymer metal-organic cage (polyMOC) gels are a relatively new class of supramolecular gels with precisely defined junction structures made possible by subcomponent assembly of nanoscale MOCs connected by polymer chains. Herein, we report that variation of the molecular weight and architecture of the polymer component of polyMOCs provides an entry into gels with ultra-high f. For example, materials with f similar to 9-12, i.e., similar to 9-12 polymer chains connect each MOC within the gel network, are realized. As a consequence of their increased f, these gels display exemplary mechanical properties at low concentrations (down to 240 mu M) of metal ions and only 5.4-5.9 wt % of polymer. Furthermore, X-ray and neutron scattering pointed to an additional level of structural hierarchy that arises from the assembly of M12L24 MOCs into clusters. The relationships between polymer and polyMOC network structure revealed here will facilitate the design of high-performance polyMOCs.