Novel CdV2O6/g-C3N4 hybrid system was synthesized by a facile mixing-calcination method. The photocatalytic test indicated that the decoration of CdV2O6 nanorods on g-C3N4 can significantly promote the photocatalytic activity in RhB degradation under visible light. The optimal CdV2O6/g-C3N4 sample exhibited a degradation rate of 0.041 min(-1), which is 4.5 times higher than that of pure g-C3N4. Various techniques including N-2 adsorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy (DRS), and photoluminescence (PL) spectroscopy were applied to investigate the origin of the enhanced photoactivity of CdV2O6/g-C3N4. The results indicated that the enhanced activities were mainly attributed to the interfacial transfer of photogenerated electrons and holes between CdV2O6 and g-C3N4, leading to the effective charge separation in the composite, which were evidenced by photoluminescence spectroscopy and photocurrent analysis. This work may provide some useful information for the future design and practical application of multifunctional hybrids photocatalysts in water purification. (C) 2016 Elsevier B.V. All rights reserved.