Conventional microbial electrolysis cell (MEC) for treating nitrobenzene (NB) suffers from insufficient mass transfer, leading to low removal efficiency. Electrochemical filtration (EF) was coupled with MEC to construct an EF-MEC system, which increased the removal rate of NB by 6.5 times in comparison with a conventional MEC. The EF process enhanced the convection mass transfer of NB and hence increased its removal. The EF process was also accompanied by a lower loading rate of NB so that 88.1% of NB in the feed could be reduced and the conversion ratio of NB to AN was high up to 98.2%. Therefore, the toxic effects on anode biofilms were relieved, leading to the enrichment of electroactive microorganisms, especially Geobacter , Desulfovibrio, and Rhodopseudomonas. The enriched anode electroactive microorganisms reciprocally promoted electrogenesis and hence the removal of NB. This EF-MEC system has functionally complemented the benefits between the EF and MEC processes, and it is very promising in treating NB-contained wastewater. [Display omitted] • Electrochemical filtration (EF) was coupled with a microbial electrolysis cell (MEC). • Nitrobenzene was rapidly reduced resulted from the enhanced mass transfer by EF. • Anode electroactive microorganisms were enriched and promoted the electrogenesis. [ABSTRACT FROM AUTHOR]