ABSTRACT The global shift toward renewable energy solutions necessitates the development of efficient electrocatalysts to overcome the limitations of current oxygen evolution reaction (OER) systems in water electrolysis. Herein, we report a hydrothermally synthesized polyoxovanadate‐based metal–organic framework, [Co (bix) 1.5 (mim)][V 2 O 6 ] (Co‐V‐MOF, bix = 1,4‐bis (imidazol‐1‐ylmethyl)benzene, mim = 1‐methylimidazole), featuring a distinctive 3D architecture with bimetal {V 4 Co 2 } inorganic layers bridged by bix ligands. Electrochemical characterization demonstrates OER activity with a low overpotential of 350 mV (at 10 mA·cm −2 in 1 M KOH), surpassing commercial RuO 2 benchmarks. The material's operational durability is evidenced by minimal potential degradation during extended testing, while its favorable charge‐transfer kinetics are reflected in a reduced Tafel slope and impedance. Complementary magnetic investigations indicate the emergence of antiferromagnetic associations at the Co 2+ nodes. This study establishes polyoxovanadate‐MOF hybrids as a new class of high‐performance electrocatalysts for sustainable energy conversion systems.