The environmentally prevalent polybrominated diphenyl ether (PBDE) #47 and polychlorinated biphenyls (PCBs) #28 and #118 were challenged for 24 hours with a novel biomass-supported Pd catalyst (Bio-Pd⁰). Analysis of the products via GC-MS revealed the Bio-Pd⁰ to cause the challenged compounds to undergo stepwise dehalogenation with preferential loss of the least sterically hindered halogen atom. A mass balance for PCB #28 showed that it is degraded to three dichlorobiphenyls (33.9%), two monochlorobiphenyls (12%), and biphenyl (30.7%). The remaining mass was starting material. In contrast, while PCB #118 underwent degradation to yield five tetra- and five trichlorinated biphenyls, no less chlorinated products or biphenyl were detected, and the total mass of degraded products was 0.3%. Although the Bio-Pd⁰ material was developed for treatment of PCBs, a mass balance for PBDE #47 showed that the biocatalyst could prove a potentially useful method for treatment of PBDEs. Specifically, 10% of PBDE #47 was converted to identifiable lower brominated congeners, predominantly the tribrominated PBDE #17 and the dibrominated PBDE #4, 75% remained intact, while 15% of the starting mass was unaccounted for.