Severe surface photocarrier recombination and poor electronic conductivity are the major factors behind the sluggish photoelectrochemical water oxidation kinetics of the ZnFe2O4 photoanode. Here, the CeOx catalyst overlayer has been coupled with the reduced ZnFe2O4 nanorods (NRs) to reduce the surface charge recombination on the photoanode significantly. The density functional theory (DFT) studies indicate that the oxygen vacancy defect‐rich CeOx catalyst constructs a favorable band alignment with ZnFe2O4 promoting rapid photocarrier separation and serves as a conducting photocarrier transfer pathway accelerating the hole transportation toward the electrode/electrolyte interface. The ZnFe2O4/CeOx nano‐heterostructure photoanode exhibits a current density of 0.64 mA cm−2 at 1.23 V versus RHE under AM 1.5 G illumination, which corresponds to >167% increase over that of the ZnFe2O4 NRs photoanode. The CeOx coupling reduces the onset potential cathodically by 180 mV over the ZnFe2O4 NRs photoanode. The ZnFe2O4/CeOx nano‐heterostructure photoanode also exhibits excellent charge transfer efficiency (≈64% at 1.23 V vs RHE) and photostability. The results indicate the superior catalytic performance of oxygen vacancy defect‐rich CeOx in the PEC process. This work demonstrates the multifunctional role of CeOx as a surface passivation overlayer, hole transfer layer, and efficient oxygen evolution reaction catalyst.

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