Photoelectrochemical (PEC) water oxidation is a highly challenging task that acts as a bottleneck for efficient solar hydrogen production. It is because each cycle of water oxidation is composed of four proton-coupled electron transfer (PCET) processes and conventional photoanodes and cocatalysts have limited roles in enhancing the charge separation and storage rather than in enhancing catalytic activity. In this study, a simple and generally applicable strategy to improve the PEC performance of water oxidation photoanodes through their modification with polyethyleneimine (PEI) hydrogel is reported. The rich amine groups of PEI not only allow the facile and stable modification of photoanodes by crosslinking but also contribute to improving the kinetics of PEC water oxidation by boosting the PCET. Consequently, the PEC performance of various photoanodes, such as BiVO4, Fe2O3, and TiO2, is significantly enhanced in terms of photocurrent densities and onset potentials even in the presence of notable cocatalyst, cobalt phosphate. The present study provides new insights into and strategies for the design of efficient photoelectrodes and PEC devices.