Porous carbon-supported CoFe-LDH-based catalysts were synthesized and utilized as excellent oxygen evolution reaction catalysts in an alkaline medium. High-resolution transmission electron microscopy images and N₂-sorption experiments suggested vertical growth of LDH on carbon support and narrow mesoporous nature of the materials, respectively. We proposed that the surface oxygen functional groups of carbon materials provided the nucleation sites for the crystal growth of the LDH on carbon support utilizing short-range electrostatic interaction, which led to vertical growth of LDH with a narrow mesoporous nature. Among the synthesized materials, CoFe-LDH/MMC showed a remarkable mass activity of 559.2 A g⁻¹, a turn-over frequency of 4.22 s⁻¹,and a massive roughness factor value of 269. This excellent reactivity has been attributed to: (a) the vertically aligned narrow mesoporous nature of the material that increased the electrolyte accessibility inside the material and thus improved active sites for catalysis, (b) the high electrical conductivity of the material and (c) increased electron contribution to the 3d orbital of cobalt from carbon weakened the Co-oxygen bond and thus further facilitated the formation of O–O bond formation and O₂ desorption during water oxidation.