A family of coordination polymers with remarkable structural and chemical complexity is produced when Cu and Zn are combined with 5-hydroxyisophthalic acid and 4,4′-bipyridyl. The structures of these four- and five-component phases are fully ordered, with the two metals occupying different sites and the ligands playing distinct bridging roles in each structure. In one five-component phase, oxalate forms as a product of partial ligand decomposition and is incorporated alongside the two original ligands into the resultant solid. The valence of Cu and the Cu/Zn ratios differ between the phases, in spite of similar synthetic conditions.