Appropriate control of energy band bending at the interface between semiconductors and electrolytes are closely related to performance of photoelectrochemical (PEC) water splitting. Dipoles formed near the surface of semiconductors induces energy band bending at the interface. Energy band bending control has been demonstrated by employing charged molecules and piezoelectric materials. However, chemical and piezoelectric approaches have demerit of chemical instability and inducement of instantaneous dipole, respectively. To overcome these problems, we adopted the ferroelectric material for PEC water splitting, where spontaneous dipoles in the material can be oriented by applying external electric field. In this work, we hydrothermally synthesized vanadium (V)-doped ferroelectric ZnO nanosheets and employed to systematically investigate the dipole effect on performance of V-doped ZnO PEC for water oxidation. Consequently, positively polarized V-doped ZnO photoanode exhibits 125% enhanced water splitting efficiency compared to negatively polarized ones due to favorable band bending for carrier transport from semiconductor to water.