Abstract: The vitrinite-rich concentrates were extracted respectively from the Datong bituminous coal and the Xinjiang bituminous coal by the density gradient centrifugation method. The activated carbons were prepared by physical activation with carbon dioxide using the above raw coals and vitrinite. The structural properties of vitrinite and the corresponding raw coals were compared, and the characteristics of crystallite and pore structure were analyzed after the carbonization and CO₂ activation process. The differences of aromatic and aliphatic hydrocarbon structures of coal and its vitrinite samples were analyzed by Fourier transform infrared spectroscopy. Microcrystalline structure parameters and aromaticity index of coals, chars and activated carbons were analyzed by X-ray diffractometer. The pore structure parameters of chars and activated carbons were studied by the low-temperature nitrogen adsorption method. Compared with raw coals, the crystallite unit sizes of vitrinite were smaller, the length of aliphatic hydrocarbon chain was shorter, and the number of branch chains was larger than those of the corresponding coals, which was beneficial to enhance the fluidity in the carbonization process. Moreover, the weight loss rates of vitrinite were higher, and the weight loss peaks were wider than that of the coals during the carbonization process by thermogravimetric analyzer. The above differences of structural properties and carbonization reactivity of coal and its vitrinite samples could affect the structure characteristics of chars. The results showed that the crystallite lamella size and stacking thickness of vitrinite chars were both increased after carbonization at 850 ℃, while the stacking thickness of crystallite in coal chars was decreased, which indicated that the differences of maceral mainly affected the vertical stacking of crystallite lamella during carbonization. Meanwhile, it led to higher aromaticity and larger BET specific surface area of both vitrinite chars. After the CO₂ activation process, the stacking thickness and lamella size of crystallite in activated carbons were lower than that of the corresponding chars, indicating that the crystallite unit got burnt by CO₂ activation. The dominant micropore structures were obtained after activation process. The BET specific surface areas of activated carbons from vitrinite reached 744.1 and 797.4 m²/g, respectively, which were significantly higher than that of activated carbons from coals. The micropore and mesopore volumes of vitrinite-based activated carbons were both higher than that of coal-based activated carbons, and the micropore volumes were 1.7−2.2 times more than that of coal-based activated carbons. The above results indicated that the chars with higher aromaticity and more porosity were beneficial to generate micropore structure during activation process.