WO3-x was deposited on TiO2(B) nanosheets prepared using TiCl4 to form layered heterostructures via a two-step solvothermal synthesis, in which the horizontal growth of WO3-x on TiO2(B) nanosheets was carried out using WCl6 and ascorbic acid as a reducer. Optimized preparation conditions allowed WO3-x/TiO2(B) layered heterostructures to be formed. The photo- and electro-chemical properties of layered heterostructures depended strongly on the amount of WO3-x. The WO3-x/TiO2(B) heterostructures demonstrated perfect catalytic performance in full solar-spectrum light and a fast degradation effect for dye and organic colorless pollutant. All target chemicals were degraded within 10 min using WO3-x/TiO2(B) samples as a photo-catalyst in the full solar-spectrum. The photo-assisted production kinetic of Cr(VI) ions were tested. The results indicate that the reproduction rate of Cr(VI) ions using WO3-x/TiO2(B) sample is three times higher than the initial TiO2 nanosheets. The result of the photo current and Mott-Shottky curve indicates that enhanced catalysis activity is ascribed to the surface of the metastable TiO2(B) with Ti3+ defects and oxygen vacancies as active sites for photocatalytic reaction. In addition, the loading of WO3-x greatly broadened the light absorption range of TiO2(B), meaning that the product responded in the full solar spectrum.