Polyaniline (PANI), with its low cost, chemical stability and high conductivity, is used as a hole transporting layer to fabricate NiOOH/PANI/BiVO4 (NPB) photoanode, of which the photoelectrochemical (PEC) water splitting performance is significantly enhanced. The remarkable water oxidation photocurrent of NPB photo anode achieves 3.31 mA cm(-2) at 1.23 V vs. RHE under AM 1.5G solar light irradiation, which is greatly increased compared with that of pristine BiVO4 (0.89 mA cm(-2) under the same condition). The maximal incident photon-to-current conversion efficiency achieves 83.3% at 430 nm at 1.23 V vs. RHE and the maximal applied bias photo-to-current efficiency reaches 1.20% at 0.68 V vs. RHE, which are nearly five and ten times higher than that of pristine BiVO4 photoanode, respectively. This NPB photoanode exhibits excellent stability with about 97.22% Faraday efficiency after PEC water splitting for 3 h. The exciting results demonstrate that PANI shows great potential as a hole-transporting layer for photoanode and NPB is an efficient and stable photoanode material with a great potential application in PEC water splitting. Overall, this work provides an excellent reference on designing and fabricating photoanode materials for the future.