The micro/nano-structured CaWO(4)/Bi(2)WO(6) composite was successfully synthesized by a one-step hydrothermal route without using any templates or surfactants. The as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-vis diffuse reflectance spectroscopy (UV-vis DRS), Fourier transform infrared (FT-IR) spectroscopy, thermogravimetry-differential scanning calorimetry (TG-DSC) and Brunauer-Emmet-Teller (BET) theory. The results indicated that the composite has a two-phase composition: CaWO(4) and Bi(2)WO(6). The photocatalytic activities of the CaWO(4)/Bi(2)WO(6) composite were evaluated for the degradation of Rhodamine B (RhB) dye and 4-nitrophenol (4-NP) in aqueous solution under visible-light irradiation (>420 nm), which were 4.5 times and 2.5 times higher than that of the pure Bi(2)WO(6), respectively. On the basis of the calculated energy band positions, the mechanism of enhanced photocatalytic activity for the micro/nano-structured CaWO(4)/Bi(2)WO(6) composite can be attributed to the effective separation of electron-hole pairs.