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This article presents a detailed structural study of a new spherical MgCl2-supported TiCl4 Ziegler-Natta catalyst for isotactic propylene polymerization, and researches on the relationship between catalyst structure and polymer proper-ties. The spherical support with the chemical composition of CH3CH2OMgOCH(CH2Cl)2has been synthesized from a new dispersion system and is used as the supporting material to prepare Ziegler-Natta catalyst. The XRD analysis indicates that the catalyst is fully activated with δ-MgCl2 in the active catalyst. The far-IR spectrometric results conifrm again the pres-ence of δ-MgCl2 in the active catalyst. Textural property of the active catalyst exhibits high surface area coupled with high porosity. The high activity in propylene polymerization is mainly ascribed to the full activation and the porous structure of the catalyst. Scanning electron microscopy/energy dispersive spectrometer mapping results indicate a uniform titanium dis-tribution throughout the catalyst particles. Particle size analysis shows that the catalyst has a narrow particle size distribu-tion. The perfect spherical shape, uniform titanium distribution and narrow particle size distribution of the catalyst conifrm the advantage of polymer particles production with less ifnes. The solid state13C NMR and mid-IR spectroscopic analyses indicate that there exists strong complexation between diisobutyl phthalate and MgCl2, which leads to the high isotacticity of polypropylene.