Photocatalytic membrane (PM) has been broadly used for industrial wastewater treatment. However, most developed photocatalytic materials are only responsive to UV-light irradiation. In this study, MoS2@WO3 composite was hydrothermally synthesized and added to PVDF membranes for rubber wastewater treatment. The diffuse reflectance spectra (DRS) results prove that the MoS2@WO3 composite is responsive to visible light irradiation with a 1.49 eV band gap. According to the SEM-EDX result, the MoS2@WO3 composite has been successfully embedded and evenly dispersed on the membrane surface and matrix. The addition of MoS2@WO3 increased the hydrophilicity of the membrane with the initial flux value up to 44.26 L·min−2·h−1 and 63.69 L·min−2·h−1 in dark and vis-light irradiation, respectively. The rejection values reached 97.04 %, 90.63 %, and 95.64 % for COD, TDS, and NH3-N, respectively, and showed excellent reusability after 5 recovery cycles upon vis-light irradiation. It has been proven that PVDF-MoS2@WO3 membrane shows the highest constant rate (k) values, 2.93 × 10−3 min−1 and 2.72 × 10−3 min−1 for COD and NH3-N, respectively. The scavenger analysis confirmed that *OH radical is the primary responsible species to organic pollutant degradation. All results have proven that MoS2@WO3 affects the membrane performance from the physical separation process through filtration and photocatalytic degradation mechanisms. Therefore, the PVDF-MoS2@WO3 photocatalytic membrane offers a promising potential to improve the performance of the existing rubber wastewater treatment.