To modify the band natures and photochemical properties of Ca2Bi2O5, partial substitutions of La3+-, Na+-, Te4+- ions on Bi-sites were respectively conducted. The phase formations were investigated via XRD Rietveld refinements. High spontaneous polarization can be induced by the special geometry of Bi-O polyhedra with seesaw -like arrangement. Ca2Bi2O5 has a band energy of 2.49 eV (498 nm) with a direct allowed transition nature. La3+-, Na+-, Te4+ -substitution can modify UV-vis absorption via the band-gap narrowing and the induced defects. Especially, the band energy of Te4+-doped Ca2Bi2O5 was reduced to 229 eV (541 nm) indicating a significant harvest of visible-light. The photocatalysis was evaluated on MB photodegradation. The impurity substitution can improve photocatalysis of Ca2Bi2O5. XPS, emission, and decay times were applied to discuss the mechanism. La3+-, Na+-, Te4+ -doping in Ca2Bi2O5 can depress the recombination of light-induced charges via prolonging the decay times. The results could be referred to investigate multifunctional optical applications of bismuth semiconductors. (C) 2020 Elsevier B.V. All rights reserved.