Reductive dechlorination is the primary pathway for environmental removal of pentachlorophenol (PCP) in soil under anaerobic condition. This process has been verified to be coupled with other soil redox processes of typical biogenic elements such as carbon, iron and sulfur. Meanwhile, biochar has received increasing interest in its potential for remediation of contaminated soil, with the effect seldom investigated under anaerobic environment. In this study, a 120-day anaerobic incubation experiment was conducted to investigate the effects of biochar on soil redox processes and thereby the reductive dechlorination of PCP under anaerobic condition. Biochar addition (1%, w/w) enhanced the dissimilatory iron reduction and sulfate reduction while simultaneously decreased the PCP reduction significantly. Instead, the production of methane was not affected by biochar. Interestingly, however, PCP reduction was promoted by biochar when microbial sulfate reduction was suppressed by addition of typical inhibitor molybdate. Together with Illumina sequencing data regarding analysis of soil bacteria and archaea responses, our results suggest that under anaerobic condition, the main competition mechanisms of these typical soil redox processes on the reductive dechlorination of PCP may be different in the presence of biochar. In particularly, the effect of biochar on sulfate reduction process is mainly through promoting the growth of sulfate reducer (Desulfobulbaceae and Desulfobacteraceae) but not as an electron shuttle. With the supplementary addition of molybdate, biochar application is suggested as an improved strategy for a better remediation results by coordinating the interaction between dechlorination and its coupled soil redox processes, with minimum production of toxic sulfur reducing substances and relatively small emission of greenhouse gas (CH4) while maximum removal of PCP.