A series of new coordination polymers and oligomers of polyimine ligands with silver(I) ions have been synthesized and characterized by single-crystal X-ray diffraction studies, elemental analysis, IR, UV−Vis, and NMR spectroscopy. They represent discrete dinuclear Ag(I) complexes, one-dimensional polymers, and two-dimensional polymeric assemblies, depending on the chosen type, functionality, and denticity of the bridging ligands. Trigonal, tetrahedral, and pseudo-tetrahedral, as well as the more common linear coordination motifs of the silver(I) ions, have been observed, demonstrating the high versatility in the supramolecular design of such hybrid organic−inorganic materials.