AbstractPalmierite Ba3V2O8 and related Cu‐ and N‐doped congeners were prepared by sol‐gel, ion‐exchange, and solid‐state reactions, respectively, with the aim of tailoring their optical, electronic, and photocatalytic properties. The catalysts were characterized by XRD analyis, UV/Vis diffuse reflectance spectroscopy, SEM with energy‐dispersive X‐ray spectroscopy, photoluminence spectroscopy, BET measurements, thermogravimetric analysis, X‐ray photoelectron spectroscopy, and TEM analysis. The electronic structures of Cu‐ and N‐doped optimal compositions were calculated theoretically on the basis of density functional theory. A series of photocatalytic degradation experiments of methylene blue under visible light irradiation disclosed the optimal dopant concentrations of Cu and N into Ba3V2O8, and the photocatalytic ability of the optimal compositions was also tested by the degradation of aniline. The differences in the degradation performance of Cu‐ and N‐doped samples are discussed on the basis of inextricably linked parameters such as photoabsorption, electronic structure, and mobility of the photoinduced charge carriers.