A novel series of inorganic–organic intercalation compounds were prepared by intercalating of alkylviologen dications into the layered vanadium pentoxide in the system of two phases of the liquid and the solid, and characterized by the techniques of X-ray diffraction (XRD), FT infrared (FTIR), X-ray photoelectron spectroscopy (XPS) and UV/vis diffuse reflectance spectroscopy (DRS).