Nature employs spontaneous self-organization of supramolecular bonds to create complex matter capable of adaptation and self-healing. Accordingly, the self-sorting of unlike ligands towards a cooperative heteroleptic complex or narcistic homoleptic association in a mixed ligand system is frequently employed to form interchangeable stimuli-responsive complex geometries with a wide range of applications. This notion is however just rarely employed in the organization of polymer networks. In this paper, we report the free-formation of heteroleptic complexes between tetra-am poly(ethylene glycol) (tetraPEG) precursors functionalized either with pyridine (tetraPy) or phenanthroline (tetraEPhen). Among a wide range of studied metal ions, tetraPy could form a network only in combination with Pd2+, presumably with a square-planar geometry, highlighting the importance of complex strength and stability in forming gels with monodentate ligands. Also, mixed networks with tetraEPhen form only in combination with Pd2+ and Fe2+, with strengths surpassing those of individual components and stabilities incomparable to those of parent networks, indicative of heteroleptic complexation. Extensive rheological, UV-vis, and DFT simulation studies revealed the coexistence of different coordination geometries, with an octahedral arrangement prevailing in the presence of Fe2+ and a square-planar geometry in the presence of Pd2+. Therefore, this study offers new opportunities for the development of stimuli-responsive topology-switching polymer networks.