Low-cost and highly efficient anode catalysts are required for the oxygen evolution reaction (OER), which is integral to the commercialization of alkaline-based water electrolysis. Herein, pore size-controlled Fe-doped Co3O4 nanostructures are prepared as non-precious metal anode catalysts using a hard-template method with silica beads of different sizes, ranging from 20 to 1000 nm in diameter. The pore size distribution and specific surface area of the catalysts are measured by nitrogen adsorption/desorption analysis and mercury intrusion porosimetry. The electrochemical properties and OER performances of the catalysts are evaluated in half and unit cells, respectively. Among the catalysts studied, FCO-T-500 synthesized using 500 nm-sized silica beads exhibits the best OER activity and stability, given by a high current density of 847 mA cm−2 at 1.8 V and superior 100 h-stability during single cell test of anion exchange membrane water electrolysis. The improved OER performance of FCO-T-500 can be attributed to the optimal pore size favorable for gas diffusion and mass transport, sufficient surface OH and H2O groups produced via KOH leaching, the largest number of electrocatalytic active sites, and the fastest charge-transfer reaction.