This paper presents a review of PCB radiolysis in oil, polar and nonpolar solvents and soil. The origins of PCB radiolysis research in alkaline isopropanol are discussed, and contrasted with radiolysis in neutral isopropanol and nonpolar solutions. Micellar solution chemistry is presented. Additionally, new applications of soil PCB radiolysis will be discussed and the effect of soil on the chemistry shown. The applicability of the extraction of PCBs from soil followed by the floatation of the solvent and subsequent radiolysis of the PCB in the floatant are reported, along with radiolysis of PCB in soil matrices.