The low efficiency of charge separation and slow kinetics of water oxidation of BiVO4 limit its application in the PEC water splitting. Here, an effective strategy is explored with Ni-doped Co3O4 (Ni/Co3O4) decorated BiVO4 photoanode by a simple route. The photocurrent of the BiVO4-Ni/Co3O4 (2.23 mA/cm2 at 1.23 VRHE biases) has significantly increased up to 4.4 times of that of bare BiVO4, and the Vonset of BiVO4-Ni/Co3O4 shows a significant negative shift (180 mV) to 0.23 V. The IPCE value of BiVO4-Ni/Co3O4 (27%, 380 nm) is about 5 times that of the BiVO4 (5%). The ηinjection and ηseparation of BiVO4-Ni/Co3O4 at 1.23 VRHE reaches 75.82% and 37.08%. The results demonstrate that the Ni/Co3O4 could enhance the charge transfer and accelerate the kinetics of water oxidation reaction, leading to the excellent PEC water splitting performance of the photoelectrode.