Antimony sulfide (Sb2S3) is an emerging photovoltaic material that comprises earth-abundant, non-toxic constituents and has a high absorption coefficient (>104 cm−1). Nevertheless, the serious bulk recombination phenomenon and the slow electrochemical reaction kinetics on the surface of Sb2S3 electrode restrict its application in the photoelectrochemical (PEC) water splitting. Herein, we have designed a polyaniline (PANI)/Sb2S3 p-n junction photoanode successfully to address these issues. With the modification of in-situ anchored PANI, the composite electrode exhibits enhanced light-absorption and accelerated charge transfer efficiency. As a result, the photocurrent density of optimized PANI/Sb2S3 photoanode is about twice of pristine Sb2S3, being a promising material for PEC water splitting.