Enhancing the ferroelectric polarization field and tuning the electron spin polarization as novel approaches to improve photocatalytic performance have sparked considerable research interest. Obviously, a straightforward strategy to simultaneously regulate ferroelectric and spin polarization will have a very attractive application prospect. In this study, a series of Bi4NbO8Cl‐Ni photocatalysts are synthesized by doping different concentrations of magnetic element Ni into ferroelectric semiconductor Bi4NbO8Cl. Due to the significant difference in atomic radius, Ni doping induces greater structural distortion and enhances the deviation of positive and negative charge centers in the crystal, thereby resulting in a stronger ferroelectric polarization field. Moreover, spin polarization is induced in the electrons, and photogenerated carriers exhibit higher spatial separation efficiency under magnetic field. Thanks to the synchronous regulation of ferroelectric and spin polarization by Ni doping, the average rates of H2 and O2 production from photocatalytic water splitting over Bi4NbO8Cl‐Ni under visible light are 342.6 and 207.1 µmol g−1 h−1, respectively, which are 10.6 and 2.7 times those of pure Bi4NbO8Cl. Notably, under an applied magnetic field of 300 mT, the average production rates are further promoted up to 616.7 and 331.4 µmol g−1 h−1. This study offers a novel strategy to significantly improve photocatalytic performance.