The p-block semiconductors are regarded as a new family of visible-light photocatalysts because of their dispersive and anisotropic band structures as well as high chemical stability. The bismuth oxide halides belong to this family and have band structures and dispersion relations that can be engineered by modulating the stoichiometry of the halogen elements. Herein, we have developed a new visible-light photocatalyst Bi24O31Cl10 by band engineering, which shows high dye-sensitized photocatalytic activity. Density functional theory calculations reveal that the p-block elements determine the nature of the dispersive electronic structures and narrow band gap in Bi24O31Cl10. Bi24O31Cl10 exhibits excellent visible-light photocatalytic activity towards the degradation of Rhodamine B, which is promoted by dye sensitization due to compatible energy levels and high electronic mobility. In addition, Bi24O31Cl10 is also a suitable photoanode material for dye-sensitized solar cells and shows power conversion efficiency of 1.5%.