Various semi-cokes were obtained from medium–low-temperature pyrolysis of Shenmu long flame coal. The combustion characteristic index and CO2 gasification reactivity of semi-cokes were measured and analyzed using thermogravimetry analysis. The influence of particle size on CO2 gasification reactivities of these semi-cokes was studied. In addition, the Brunauer–Emmett–Teller surface area (SBET), carbon material structure order and carbon crystalline structure were examined by N2 adsorption, Raman spectroscopy and powder X-ray diffraction. All of these properties were used to evaluate the CO2 gasification reactivity of these semi-cokes. The results show that the gasification reactivity of semi-cokes decreases with an increasing crystallinity and structure order. Surface area of the pores is proportional to the reactivity of the semi-coke; the greater the surface area, the faster the gasification reaction rate.