Biochar has received increasing attention for its multifunctional applications as a soil amendment. The dual effect of biochar on reductive organic pollutants and soil biogeochemical processes under anaerobic environments in parallel has yet to be fully explored. In this study, anaerobic batch experiments were conducted to examine the effect of biochar on both reductive transformation of pentachlorophenol (PCP) and soil redox processes in flooded soil. Compared to biochar-free controls, the reductive dechlorination of PCP was significantly inhibited following biochar addition, with the inhibition degree increased with increasing amount of biochar. Dissimilatory iron and sulfate reduction, as well as the production of methane, were significantly enhanced following biochar addition. The bacterial and archaeal communities showed a functional selection responded to the addition of biochar and PCP, with the core functional groups at the genus level including Dethiobacter, Clostridium, Geosporobacter, Desulfuromonas, Desulfatitalea, and Methanosarcina. These findings indicated that biochar could affect soil microbial redox processes and may act as an electron mediator altering electron distribution from PCP dechlorination to the predominant soil reduction processes, and increase understanding regarding biochar's comprehensive effects on the remediation of natural flooded soil polluted by chlorinated organic pollutants that can be degraded reductively.