Natural attenuation of polychlorinated biphenyls (PCBs) by indigenous bacteria is an effective remediation strategy for polluted marine sediments. This study investigated the relationships between PCB concentrations in sediment pore water, humin electron transfer capacity, and potential PCB dechlorinators at eight sediment sampling sites in the southern Yellow Sea, China, with differential PCB contamination. Station A2 showed the highest PCB concentration (453.16 ng L⁻¹ for seven indicator PCBs), especially of less chlorinated PCB congeners (≤5 Cl atoms), humin redox activity, and Dehalococcoides abundance (p < 0.05). Statistical analyses revealed a highly positive correlation between Dehalococcoides abundance and PCB concentration (r = 0.836, p < 0.05) and the electron shuttling ability of humins (r = 0.952, p < 0.01), whereas this was not observed for total bacteria and other potential PCB dechlorinators, e.g., Dehalobacter and Dehalogenimonas. Based on these results, Dehalococcoides might play an important role in the in situ reductive dechlorination of PCBs involving humins in marine sediments, and the natural microbial PCB attenuation capacity at station A2 was high. Chemical characterizations, electrochemical properties, and Fourier transform infrared analysis suggested that humins at station A2 had the highest electron transfer capacity. Furthermore, quinones are likely to be the functional groups that shuttle electrons during PCB dechlorination. Overall, this study provides a useful foundation for evaluating the natural microbial attenuation potential and fates of PCBs in marine sediments and for determining the role of humins as redox mediators in in situ PCB dechlorination by putative indigenous dechlorinators.