For enhanced dechlorination of 2,4-dichloronitrobenzene (2,4-DClNB), a coupled microbial electrosynthesis-upflow anaerobic sludge reactor (MES-UASB) was established, and the effect of cathode potential on the performance of combined process was investigated in this study. Results showed that a higher dechlorination efficiency of 78.5 +/- 6.1% was achieved in the coupled MES-UASB at -660 mV, and the degradation rate of 4-chloroaniline (4-ClAn) reached 4.61 mg.L-1.d(-1) within 120 h at -660 mV of cathode potential in batch experiments. The results of Illumina sequencing indicated that the biocathode operated at a lower potential favored the enrichment of dechlorination-related microbes such as Dehalobacter, Dehalococcoides and Anaeromyxobacter both in granular sludge and cathode biofilm. It could be speculated that a lower cathode potential is more feasible for the dechlorination of 2,4-DClNB due to the enrichment of dechlorination-related microbes as well as the production of electrons with higher energy for long-distance electron transfer (LDET).