An anaerobic incubation was launched with varying nitrate (1, 5, 10 and 20 mM exogenous NaNO3) and molybdate (20 mM Na2MoO4, a sulfate-reducing inhibitor) additions to investigate the characteristics of PCP dechlorination, as well as the reduction of natural co-occurring electron acceptors, including NO3-, Fe(III) and SO42-, and the responses of microbial community structures under a unique reductive mangrove soil. Regardless of exogenous addition, nitrate was rapidly eliminated in the first 12 days. The reduction process of Fe(III) was inhibited, while that of SO42- reduction depended on addition concentration as compared to the control. PCP was mainly degraded from orth-position, forming the only intermediate 2,3,4,5-TeCP by anaerobic microbes, with the highest PCP removal rate of average 21.9% achieved in 1 and 5 mM NaNO3 as well as 20 mM Na2MoO4 treatments and the lowest of 7.5% in 20 mM NaNO3 treatment. The effects of nitrate on PCP dechlorination depended on addition concentration, while molybdate promoted PCP attenuation significantly. Analyses of the Illumina sequencing data and the relative abundance of dominant microorganisms indicated that the core functional groups regulated PCP removal at genera level likely included Bacillus, Pesudomonas, Dethiobacter, Desulfoporosinus and Desulfovbrio in the nitrate treatments; while that was likely Sedimentibacter and Geosporobacter_Thermotalea in the molybdate treatment. Nitrate supplement but not over supplement, or addition of molybdate are suggested as alternative strategies for better remediation in the nitrate-deficient and sulfur-accumulated soil ecosystem contaminated by PCP, through regulating the growth of core functional groups and thereby coordinating the interaction between dechlorination and its coupled soil redox processes due to shifts of more available electrons to dechlorination. Our results broadened the knowledge regarding microbial PCP degradation and their interactions with natural soil redox processes under anaerobic soil ecosystems.