A new PVDF composite cathode membrane (PCCM) with electro-deposited Pd-rGO on PVDF/carbon fiber cloth, abbreviated as Pd-rGO PCCM, was developed. The as-prepared Pd-rGO PCCM was characterized by SEM, TEM and XRD. And it was further used in membrane bioreactor (MBR)/microbial fuel cell (MFC) coupled wastewater treatment system. The results indicated after electro-deposition, the Pd-rGO was uniformly distributed on the surface of PCCM. Under 15 cycled Pd electro-deposition on carbon fiber cloth, the Pd-15-rGO PCCM exhibited the highest catalytic activity compared to other cycles, and the optimized deposition density of rGO and Pd were 0.124 mg cm(-2) and 2.31 mg cm(-2) respectively. Under an electric field of -0.4 V cm(-1), the Pd-15-rGO PCCM showed approximately 1.9 times improvement of stable membrane flux (128-130 Lm(-2) h(-1)) compared to the condition without electric field (66 Lm(-2) h(-1)). In MBR/MFC wastewater treatment system, using Pd-15-rGO PCCM as cathode membrane, the maximum power density was 1210 mW m(-3), approximately 3.8 times higher than using initial PCCM (312 mW m(-3)). Moreover, The Pd-15-rGO PCCM in MBR/MFC coupled system showed excellent contaminants removal rates towards both traditional organic contaminants (COD at 90% and NH4+-N at 81%) in sewage and trace persistent contaminants (i.e. PAHs and phenols) in the effluent of coking wastewater.