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In order to enhance the productivity of methane from the waste activated sludge (WAS), a coupled system of microbial electrolysis cell (MEC) and anaerobic digestion (AD) was proposed. In this study, alkali, ultrasound-alkali, high-temperature coupled microaeration (TM) were applied as pretreatment methods to disintegrate the WAS flocs and break bacterial cell. After ultrasound-alkali pretreatment, the maximum accumulated concentration of VFAs and SCOD increased by 6.4 and 13.8 times compared with the initial concentration, which were 2.8 and 2.6 times of alkali pretreatment, and 2.1 and 2.1 times of TM pretreatment. Then, the pretreated sludge was transferred into MEC-AD coupled reactors and control group of AD reactors. The results showed that, methane production rate was enhanced to 0.15 m3 CH4/m3 reactor/d in the coupled reactors, which was improved by 3 times compared with control AD (0.05 m3 CH4/m3 reactor/d). The methane yield of MEC-AD coupled reactors achieved 808 ± 8 mL, which were increased by 97.0% ± 1.85% compared to control AD (410 mL). Using MEC can promote the rate of organics degradation and methane yield. The MEC-AD coupled system realized a good performance on the treatment of WAS and improved the efficiency of methane production.