Developing a semiconductor-based heterostructure photoanode is crucial in improving the photoelectrocatalytic (PEC) efficiency for degrading refractory organic pollutants. Nevertheless, the PEC performance of the photoanodes is usually restricted by electron/hole pair recombination, oxygen evolution, and slow electron transfer. Herein, a novel CoO@BiVO4 nanowire array film (Ti/CoO@BiVO4) with n-type semiconductor characteristics was prepared via a straightforward hydrothermal method. The optimized Ti/CoO@BiVO4 electrode exhibited excellent PEC decolorization efficiency of active brilliant blue KN-R (∼92.8%) and long-term stability, outperforming recent reports. The insight reason for enhancing the PEC degradation efficiency of the Ti/CoO@BiVO4 electrodes can be attributed to the large electrochemical active area, low charge transfer resistance, and negative flat band potential. The formation of a type-II heterostructure was investigated between CoO and BiVO4 further to promote the generation and separation efficiency of electron/hole pairs, indicating that the optimized Ti/CoO@BiVO4 electrode has the potential for the water PEC degradation ability and superior service life.