Bismuth layered structure materials with Aurivillius phase usually show amazing structure and physical properties. The influence of La and Ni doping on the structure, ferroelectricity and photocatalytic performance of Bi7Ti3Fe3O21 (BTF), Bi5.6La1.4Ti3Fe3O21 (La: BTF), Bi7Ti3Fe2.4Ni0.6O21 (Ni: BTF) and Bi5.6La1.4Ti3Fe2.4Ni0.6O21 (La, Ni: BTF) ceramics are explored. The enhancement of La: BTF ferroelectricity is due to the reduction of leakage current and oxygen vacancies. Co-doped La, Ni: BTF has the highest degree of ferroelectric polarization due to the large distortion of the lattice structure. La: BTF has the highest photocatalytic degradation efficiency for methylene blue (MB) dye. The reduction of grain radius, band gap and enhancement of ferroelectric polarization play a vital role in improving photocatalytic efficiency. Ni doping suppresses photocatalysis of BTF to some extent.