Poor photoelectrochemical (PEC) degradation performance of BiVO4 photoelectrode is generally caused by poor photogenerated charge carriers separate, apparent recombination, and sluggish carrier transfer mobility. To address the aforementioned issues, we first devised a method that combines oxygen vacancy (Ov) and cocatalyst FeOOH for synergistically enhanced BiVO4 PEC degradation performance. With the addition of Ov produced by the convenient hydrothermal method, the improved current density value of 0.54 mA/cm2 was attained on the BiVO4-Ov sample, which is 1.38 times higher than pristine BiVO4 at the same voltage of 1.23 V vs. RHE. Specially, the as-prepared BiVO4-Ov/FeOOH demonstrates a fascinating current density of 1.18 mA/cm2 under light, and present the largest degradation activity of 85%, which is in line with expectations. In summary, our findings show that the Ov may be efficiently protected by covering a FeOOH ultrathin nanolayer, resulting in a photoelectrode with elevated current density and stability.