A series of layered-structure Bi-based oxychlorides such as BiOCl, Bi3O4Cl, Na0.5Bi1.5O2Cl, Bi4NbO8Cl and MBiO2Cl (M = Ca, Sr, Ba, Cd, Pb) used as efficient photocatalysts. Among them, Bi3O4Cl (Eg = 2.79 eV), Na0.5Bi1.5O2Cl (Eg = 3.03 eV), Bi4NbO8Cl (Eg = 2.38 eV) and PbBiO2Cl (Eg = 2.45 eV) are visible-light-responsive. The powders synthesized by solid state reactions were characterized by X-ray diffraction (XRD) and UV-Vis diffuse reflection spectrum. Their photocatalytic activities were evaluated by the degradation of methyl orange. The results generally show that the UV-induced photocatalytic performances of the novel oxychloride catalysts are better than or comparable to that of anatase TiO2. The high photocatalytic performance of Bi-based oxychlorides is mainly ascribed to the presence of strong internal static electric fields between layers.