Different voltages were applied to anaerobic treatment to investigate the enhancement effects and the changes of microbial community structure. The results indicated that the best appropriate voltage was 0.10 V, COD removal increased by 16.72% at first 6 h and cumulative CH production increased by 23.39%. Average methane yield was 15.69% higher than that of control. The sludge measurements indicated that voltage addition could promote the interspecies electron transfer to produce more methane. The strengthening effect of voltage could be sustained for a short period of time when the voltage was removed. Microbial community analysis revealed that the changes of Methanothrix and Methanolinea resulted in higher biogas production. The increases of Smithella and Geobacter improved the possibility of “electronic syntrophism” between microorganisms and promoted the performance of DIET process. The results would provide the theoretical supports for enhancing the anaerobic treatment efficiency by voltages.Copyright © 2020 Elsevier Ltd. All rights reserved.