The presence of mixed microplastics (MPs) in anaerobic wastewater treatment processes has been shown to impede fermentation performance by suppressing microbial activity. Microbial electrosynthesis (MES), with its extensive potential, offers a promising solution for refractory substances management and methane recovery, achieved through the enhancement of microbial metabolism and interspecies electron transfer. This study, therefore, delves into the functional impacts and the microbial response to MES in the remediation of wastewater contaminated with mixed-MPs. Results indicated that mixed-MPs could inhibit methane production (−52.38%) and substance removal (−26.59%), and MES could effectively mitigate this inhibitory effect (−22.86%, −19.01%). Concurrently, MES also boosts enzymatic activities pivotal for electron transfer, such as cytochrome c and nicotinamide adenine dinucleotide (NADH), as well as those linked to energy metabolism like adenosine triphosphate (ATP). Furthermore, MES bolsters microbial resistance to mixed-MPs, as evidenced by an increase in extracellular polymeric substances (EPS), albeit with a minor rise in reactive oxygen species (ROS) production and lactate dehydrogenase (LDH) release. Correspondingly, electric stimulation promoted the enrichment of functional microorganisms associated with fermentation, acetate production, electrogenesis, and methanogenesis, and stimulated elevated expression levels of genes related to methane metabolism. Notably, the Methanothrix-mediated acetoclastic pathway emerges as the predominant methanogenic route, succeeded by the Methanobacterium-driven hydrogenotrophic pathway. Lastly, the study underscores the supportive role of applied voltage and carriers in energy metabolism and substance transport, which are associated with methanogenesis. Overall, MES demonstrates efficacy in mitigating the biotoxicity induced by mixed-MPs exposure and in enhancing anaerobic wastewater treatment and methane recovery.