Methanogenesis is commonly mass-produced under anaerobic conditions and serves as a major terminal electron accepting process driving the degradation of organic biomass. In this study, a cofactor of methanogenesis (coenzyme M, CoM) and a classic methanogensis inhibitor (2-bromoethanesulfonate, BES) were added at different concentrations to investigate how methanogenesis would affect PCP degradation in flooded soil. Strikingly, the processes of methanogenesis and PCP degradation were simultaneously promoted with CoM, or inhibited with BES, significantly (p < 0.05). High-throughput sequencing for soil bacterial and archaeal community structures revealed that members of Desulfitobacterium, Dethiobacter, Sedimentibacter, Bacillus and Methanosarcina might act as the core functional groups jointly perform PCP degradation in flooded soil, possibly through assisting microbial mediated dechlorination in direct organohalide-respiration, and/or indirect cometabolization in complex anaerobic soil conditions. This study implied an underlying synergistic coupling between methanogenesis and dechlorination, and provided insights into a novel consideration with respect to coordinating methanogenesis while promoting anaerobic degradation of PCP for complex polluted soil environment, which is necessary for the improved all-win remediation.