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A novel method in situ chlorinating-graft copolymerization (ISCGC) of grafting maleic anhydride (MAH) on isotactic polypropylene (iPP) in gas-solid phase was investigated in this paper. Chlorine (Cl-2) was used as initiator, chlorinating agent and termination agent at the same time during the reaction. The iPP was chlorinated as well as grafted with MAH in the reaction process. The product with chlorine and MAH in the same molecule was named as PP-cg-MAH. Existence of PP-cg-MAH was identified by Fourier transform infrared. Thermal behavior and crystallinity of PP-cg-MAH were analyzed by differential scanning calorimetry, X-ray diffraction and polarizing microscope. Influencing factors for the value of graft degree were also discussed. Compared with conventional peroxide initiated graft method, ISCGC revealed higher MAH graft efficiency (33%), and particularly alleviated degradation of iPP. iPP could be grafted successfully and without changing physical properties dramatically through this method.