We report herein the synthesis, structural characterization and electrocatalytic properties of three new coordination polymers, resulting from the combination of divalent metal (Ca²⁺, Cd²⁺ or Co²⁺) salts with (2-carboxyethyl)(phenyl)phosphinic acid. In addition to the usual hydrothermal procedure, the Co²⁺ derivative could also be prepared by microwave-assisted synthesis, in much shorter times. The crystal structures were solved by ab initio calculations, from powder diffraction data. Compounds M^II[O₂P(CH₂CH₂COOH)(C₆H₅)]₂ {M = Cd (1) or Ca (2)} crystallize in the monoclinic system and display a layered topology, with the phenyl groups pointing toward the interlayer space in a interdigitated fashion. Compound Co₂[(O₂P(CH₂CH₂COO)(C₆H₅)(H₂O)]₂·2H₂O (3) presents a 1D structure composed of zig-zag chains, formed by edge-sharing cobalt octahedra, with the phenyl groups pointing outside. Packing of these chains is favored by hydrogen bond interactions via lattice water molecules. In addition, H-bonds along the chains are established with the participation of the water molecules and the hydrophilic groups from the ligand. However, the solid exhibits a low proton conductivity, attributed to the isolation of the hydrophilic regions caused by the arrangement of hydrophobic phenyl groups. Preliminary studies on the electrocatalytic performance for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) have been conducted for compound 3 and its pyrolytic derivatives, which were previously thoroughly characterized. By comparison, another Co²⁺ phosphinate, 4, obtained by microwave-assisted synthesis, but with distinct stoichiometry and a known structure was also tested. For the OER, the best performance was achieved with a derivative of 3, prepared by heating this compound in N₂ at 200 °C. This derivative showed overpotential (339 mV, at a current density of 10 mA cm⁻²) and Tafel slope (51.7 mV dec⁻¹) values comparable to those of other Co²⁺ related materials.