Particulate solid solutions Bi(1-x)Ni(x)VO(4-y) were synthesized by solid-state reaction at high temperature. The samples were characterized by X-ray Diffraction (XRD), Field-Emission Scanning Electron Microscopy (FE-SEM), Energy Dispersive Spectrometer (EDS), Brunauer-Emmett-Teller (BET) surface area and Ultraviolet-Visible spectroscopy (UV-Vis). The photocatalytic activity of BiVO4 for photocatalytic degradation of organic contaminants ability in visible light region could be improved by doping of Ni(2+). The high visible light photocatalytic activity of Bi(1-x)Ni(x)VO(4-y) solid solution might be due to the generation of a new band gap and expanding the range of visible light response. It was suggested that the Ni(2+) doping was beneficial to effective charge separation of Bi(1-x)Ni(x)VO(4-y) solid solution, thus improved the photocatalytic activity.