The crystal structure, band structure, density of states, Mulliken charge, bond population and optical properties for LiBi_（1-x）M_xO_3（M=V, Nb, and Ta） were investigated using hybrid density functional theory. It was found that LiBiO_3 doped with V, Nb, and Ta presented distinctly stronger covalent interactions in M-O（M=V, Nb, and Ta） than Bi-O, thus resulting in mild distortion of the structure and facilitating the separation of photogenerated carriers. Furthermore, the hybridizations of Bi-6s, M-d（M=V, Nb, and Ta） and O-2p widened the valence and conduction bands, which promoted transmission of photogenerated carriers in the band edge and thus caused better photocatalytic performance.
