We present the synthesis and characterization of alkali metal salts of the new tetraanionic, tetrapodal ligand 2,2'-(pyridine-2,6-diyl)bis(2-methylmalonate) (A(4)[PY(CO2)(4)], A = Li+, Na+, K+, and Cs+), via deprotection of the neutral tetrapodal ligand tetraethyl 2,2'-(pyridine-2,6-diyl)bis(2-methylmalonate) (PY(CO2Et)(4)). The [PY(CO2)(4)](4) ligand is composed of an axial pyridine and four equatorial carboxylate groups and must be kept at or below 0 degrees C to prevent decomposition. Exposing it to a number of divalent first-row transition metals cleanly forms complexes to give the series K-2[(PY(CO2)(4))M(H2O)] (M = Mn2+, Fe2+, Co2+, Ni2+, Zn2+). The metal complexes were comprehensively characterized via single-crystal X-ray diffraction, H-1 NMR and UVvis absorption spectroscopy, and cyclic voltammetry. Crystal structures reveal that [PY(CO2)(4)](4) coordinates in a pentadentate fashion to allow for a nearly ideal octahedral coordination geometry upon binding an exogenous water ligand. Additionally, depending on the nature of the charge-balancing countercation (Li+, Na+, or K+), the [(PY(CO2)(4))M(H2O)](2) complexes can assemble in the solid state to form one-dimensional channels filled with water molecules. Aqueous electrochemistry performed on [(PY(CO2)(4))M(H2O)](2) suggested accessible trivalent oxidation states for the Fe, Co, and Ni complexes, and the trivalent Co3+ species [(PY(CO2)(4))Co(OH)](2) could be isolated via chemical oxidation. The successful synthesis of the [PY(CO2)(4)](4) ligand and its transition metal complexes illustrates the still-untapped versatility within the tetrapodal ligand family, which may yet hold promise for the isolation of more reactive and higher-valent metal complexes.