One-step introduction of metallic Bi, non-metallic C into Bi2WO6 was successfully prepared via a facile hydrothermal synthetic route. The obtained materials were characterized by X-ray diffraction, scanning electron microscope, transmission electron microscope, X-ray photoelectron spectroscopy (XPS), nitrogen absorption–desorption isotherms, photoluminescence spectroscopy, photocurrent responses, electrochemical impedance spectroscopy (EIS), electron paramagnetic resonance (EPR), UV–vis diffuse reflectance spectra (DRS). As a result, C/Bi codecorated Bi2WO6 shows profoundly photocatalytic activity in comparison with undoped Bi2WO6 for decomposition of various industrial pollutants, including phenol, ciprofloxacin, bisphenol A, rhodamine B, and methyl orange under visible light (λ ≥ 420 nm). The enhanced photocatalytic properties may be ascribed to the fact that the synergistic effects of the SPR effect of Bi metal and the hybrid orbital constructed by C doping not only enhance the absorption of visible light but also accelerate the separation and migration of photo-generated carriers. Moreover, on the basis of the radical species trapping experiments, EPR analyses, DRS technique and Mott–Schottky plots, we proposed a simple photocatalytic mechanism.