In addition to molecular interaction and physical entanglement of the molecular chains across the interface in poly(vinyl chloride)-nitrile rubber joints, at high temperatures and long contact times interfacial chemical bonds may be formed which seem to couple the two adherends thereby resulting in cohesive failure of the rubber matrix on peeling. This is verified by performing the peel tests at high temperatures, low peel rates and under swollen conditions. Infrared spectroscopic studies of the PVC/NBR blend reveal the formation of chemical bonds at the contact temperatures studied. The peel fracture energy is found to depend on the acrylonitrile content and presence of carboxylic content in the NBR, and the presence of stabilizer and plasticizer in the PVC phase, in addition to the molding and testing conditions.