Radiolytic (electron beam) and photolytic (ultraviolet, UV) dechlorination of polychlorinated biphenyls (PCBs) in a marine sediment are described. Samples of a PCB-laden marine sediment, Standard Reference Material (SRM) 1944, NewYork/New Jersey Waterway Sediment, have been mixed with aqueous alcohol solutions and irradiated with an electron beam or photolyzed. Additives, such as alcohol, enhance the radiolytic yield and PCB dechlorination. In the electron beam irradiated samples, the concentrations of 29 PCB congeners decrease with irradiation dose. At the highest dose (500 kGy), the total concentration of PCBs is decreased by 83%. Photolysis leads to little dechlorination, but photolysis with added triethylamine leads to dechlorination (about 60%). It is likely that photolysis under optimal conditions (other additives, exposure time) may be as effective as electron beam radiolysis for the dechlorination of PCBs in sediment.