Searching earth-abundant materials for photocatalytic fuel cells (PFCs) remains an important goal for energy conversion and storage, and the construction of semiconductor composite materials is an effective method to improve the photochemical properties of photoelectrodes in PFCs. Herein, a simple hydrothermal method is used to load an Fe 2 O 3 layer on a BiVO 4 film for use in the photoanode of a PFC, and the electrochemical results show that the short-circuit current density (J sc ) and the open-circuit voltage (V oc ) of the PFC reach 3.05 mA/cm 2 and 0.84 V under simulated solar irradiation, respectively. Furthermore, a detailed analysis of the density of states, charge density difference, and work functions of the Fe 2 O 3 /BiVO 4 heterojunction is discussed by the density functional theory (DFT) method, showing the proper band alignment and the existence of a built-in electric field at the interface with the direction from BiVO 4 to Fe 2 O 3 , which greatly improves the performance of the PFC. This research provides a clear mechanism for the Fe 2 O 3 /BiVO 4 heterojunction in the PFC system.