CuS-WO3 composites were synthesized by an in situ solution method at low temperature. The crystalline phase, morphology, particle size, and the optical properties of CuS-WO3 samples were characterized by XRD, SEM, XPS, and UV-vis diffuse reflectance spectra. CuS-WO3 composites showed much higher activity for photocatalytic degradation of RhB as compared with WO3 and CuS. The degradation rate constant over 1 wt% CuS-WO3 catalyst was 4.4 times and 9.2 times higher than that of WO3 and CuS, respectively. It is found that holes (h(+)) and superoxide radical anions (. O-2(-)) are the dominant reactive species by using methanol, disodium ethylenediaminetetraacetate (EDTA) and ascorbic acid as scavengers. Band structure analysis shows that bottom of CB of WO3 is very similar with and higher (ca. 0.01 eV) than the top of VB of CuS. The results of PL showed that the similarity renders the recombination between photogenerated holes on the VB of CuS and photogenerated electrons on the CB of WO3 possible and easy, forming a direct Z-scheme in CuS-WO3. This result in that more electrons in the CB of CuS and holes in the VB of WO3 survived, and then participated in the photocatalytic degradation of RhB, showing an increased activity. (c) 2017 Elsevier B.V. All rights reserved.