Chemical crosslinked poly(vinyl chloride) (C-PVC) was synthesized by vinyl chloride suspension polymerization in the presence of diallyl phthalate (DAP) and plasticized to prepare poly(vinyl chloride) (PVC) thermoplastic elastomer (TPE) materials. The chemical crosslinking and physical crosslinking structure in chemical crosslinked PVC-TPE were investigated. It showed that the gel fraction and the crosslinking density of gel increased as the feed concentration of DAP increased. C-PVC prepared by VC/DAP copolymerization was lightly crosslinked as compared with irradiation crosslinked PVC. Physical entanglements would greatly influence the crosslinking density of gel when the gel fraction was high. Chemical crosslinking had little influence on the recrystallization behavior of PVC. A structure model of chemical crosslinked PVC-TPE was proposed, in which chemical networks acted with physical networks cooperatively. It also showed that chemical crosslinking and physical crosslinking influenced the processability and mechanical properties of chemical crosslinked PVC-TPE cooperatively. Although the processability of PVC-TPE deteriorated with chemical crosslinking, the dimension stability and elasticity of PVC-TPE were improved as the permanent chemical networks were introduced. (C) 2000 John Wiley & Sons, Inc.