A novel fly ash cenospheres supported Pt–BiVO4 composites (Pt–BiVO4/FACs) photocatalysts were prepared by modified metalorganic decomposition process, followed by photochemical reduction. The composites were characterized by X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), and UV–vis diffused reflectance spectroscopy (DRS) techniques. The results indicate that the visible light absorption of the Pt–BiVO4/FACs composite is greatly enhanced. The Pt element is present in the metallic form and disperses in the composite samples. Photocatalytic activities of the Pt–BiVO4/FACs composites were evaluated by the methylene blue (MB) degradation under visible light irradiation. The results indicate that the photocatalytic efficiency is significantly improved after the Pt species was loaded and the 2 wt% Pt-loaded composite showed the highest photocatalytic activity.