Asymmetric double cantilever beam and peel test experiments were completed to evaluate the ability of chlorinated polyethylenes to compatibilize poly(vinyl chloride) (PVC) and polyolefin elastomer (POE) blends. A series of chlorinated polyethylenes that are blocky in nature (bCPEs) with varying composition (% chlorine) and molecular weight (melt index) were compared to one chlorinated polyethylene, where the chlorine is randomly distributed throughout the chain (rCPE). Results indicate that improvement in the interfacial adhesion between the PVC and the POE is dramatically more pronounced with the bCPEs than with the rCPE. In addition, the optimum bCPE composition was determined to be 20% chlorine and the interfacial adhesion force was found to increase with increasing molecular weight. Finally, the POE/CPE, interaction was found to govern the ability of the chlorinated polyethylene to compatibilize PVC and POE.