Four transition metal formate coordination polymers with anionic frameworks, namely, Na[Mn(HCOO)(3)], K[Mn(HCOO)(3)], Na-2[Cu-3(HCOO)(8)], and K-2[Cu-5(HCOO)(12)], were synthesized using a mild solution chemistry approach. Multitemperature single-crystal (100-300 K) and powder Xray diffraction studies of the compounds reveal structures of large diversity ranging from cubic chiral Na-Mn formate to triclinic Na-Cu formate. The structural variety is caused by the nature of the transition metals, the alkali metal ion templation, and the versatility of the formate group, which offers metal metal coordination through three different O-C-O bridging modes (syn-syn, syn-anti, anti-anti) in addition to metal metal bridging via a single oxygen atom. The two manganese(II) compounds contain mononuclear, octahedrally coordinated moieties, but the three-dimensional connectivity between the manganese octahedra is very different in the two structures. The two copper frameworks, in contrast, consist of binuclear and mononuclear moieties (Na-Cu formate) and trinuclear and mononuclear moieties (K-Cu formate), respectively. Procrystal electron density analysis of the compounds indicates one-dimensional K+-ion conductivity in K-Mn and K-Cu, and the nature of the proposed potassium ion migration is compared with results from similar analysis on known Na+ and K+ ion conductors. K-Mn and Na-Mn were tested as cathode materials, but this resulted in poor reversibility due to low conductivity or structural collapse. The magnetic properties of the compounds were studied by vibrating sample magnetometric measurements, and their thermal stabilities were determined by thermogravimetric analysis and differential thermal analysis. Despite structural differences, the metal formates that contain the same transition metal have similar magnetic properties and thermal decomposition pathways, that is, the nature of the transition metal controls the compound properties.