Photoelectrochemical (PEC) water splitting serves as one of the promising approaches for producing clean and renewable energy, and their solar-hydrogen energy conversion efficiency depends on the interfacial charge separation and carrier mobility. Herein, we report an effective strategy to promote the PEC performance by fabricating a WO3 photoanode rich in oxygen vacancies (Ov) modified by NiFe-based layered double hydroxide (LDH). When WO3-Ov/NiFe-LDH is used as a photoanode, the maximum photocurrent density at 1.8 V versus RHE has been significantly enhanced to 2.58 mA·cm-2, which is 4.3 times higher than that of WO3. In addition, analogues were studied in controlled experiments without Ov, which further demonstrated that the synergistic effect of NiFe-LDH and Ov resulted in increased carrier concentration and driving force. According to electrical impedance spectroscopy, X-ray photoelectron spectroscopy, and Mott-Schottky analysis, the built-in electronic field in WO3 homojunction, along with the accelerated hole capture by the NiFe-LDH cocatalyst contributes to the improved charge separation and transport in the WO3-Ov/NiFe-LDH electrode. This work proposes an efficient and valuable strategy for designing the structure of WO3-based photoelectrodes.