Coupled Bi2O3/TiO2 photocatalysts were fabricated by sol-gel and hydrothermal methods and characterized using various spectroscopy techniques. Photocatalytic reduction of Cr(VI) in aqueous solution, together with the synergistic effect of photodegradation of bisphenol A (BPA), was investigated using these coupled Bi2O3/TiO2 under visible-light irradiation. Coupling of Bi2O3 inhibited the phase transformation from anatase to rutile and extended absorption region to visible light. Bi ions did not enter TiO2 lattice and were more likely to bond with oxygen atoms to form Bi2O3 on the surface of TiO2. Photovoltage signals in visible range revealed the effective interfacial charge transfer between Bi2O3 and TiO2. Two percent Bi2O3/TiO2 exhibited the highest photocatalytic activity of visible-light-induced reduction of Cr(VI). The addition of BPA effectively increased the photocatalytic reduction of Cr(VI). Simultaneously, the presence of Cr(VI) promoted the degradation of BPA, which was demonstrated by the investigation of TOC removal yield and generated intermediates. A possible mechanism of photocatalytic reduction of Cr(VI) and degradation of BPA in Bi2O3/TiO2 system was proposed. The synergistic effect, observed between reduction of Cr(VI) and degradation of BPA, provides beneficial method for environmental remediation and purification of the complex wastewater.