Abstract: The structure-performance research in Ziegler-Natta catalyst is based on the detailed characterization of chemical and physical properties of complicated components and their interactions system. Therefore，this paper reviews the advances in the research of characterization for Ziegler-Natta catalysts used in alkene polymerization since the very beginning of Ziegler-Natta catalysts in 1950’s. The apparatus usually used and corresponding research of each instrument are introduced，including X-ray diffraction（XRD），electron paramagnetic resonance/electron spin resonance（EPR/ESR），nuclear magnetic resonance（NMR），infrared spectroscopy（IR），Raman spectroscopy（Raman），X-ray photoelectron spectroscopy（XPS），electron microscope（EM），thermo-gravimetric analysis/differential scanning calorimetry（TG/DSC）and etc. Prospect of characterization research in this field is briefly discussed.