Recent papers have confirmed current environmental pollution and the continuous release of polychlorinated biphenyls (PCBs) despite the prohibition of its manufacture worldwide. As the dehalogenating microorganisms are able to remove halogens from various analogous compounds, the characterization of PCB metabolisms can improve the degradation of similar compounds. Thus, this study extensively evaluated the microbial community developed in methanogenic and iron-reducing reactors. The horizontal-flow anaerobic reactor (HAIB) with real waste of Aroclor (1 mL L) was fed with mineral medium, ethanol, and sodium formate. Bacteria belonging to Thermotogaceae (Thermotogae), Geobacteraceae, Chloroflexi, Proteobacteria, and Firmicutes (Clostridium) were identified in the HAIB reactor. Bacteria belonging to the Chloroflexi, Firmicutes, and Geobacteraceae are associated with the degradation of hydrocarbons and could be related to the Aroclor waste in this paper. Furthermore, 5.26 × 10 cells gTVS of iron-reducing bacteria were quantified by the most probable number method in the HAIB reactor, suggesting that this group has an important role in aromatic degradation. Moreover, the evaluation of methanogenic and iron-reducing microorganisms in batch reactors with Aroclor 1260 was performed and the biomass growth was not affected by the addition of PCB. The methane production reached 0.38 µmol CH gTVS and the iron reduction attained 90% in batch reactors. Through microbial analyses from HAIB and batch reactors, lower diversity was evidenced in the presence of PCB. This paper indicates the relevant role of iron-reducing organisms and Chloroflexi, Geobacteraceae, and Firmicutes group in PCB metabolism.