Interaction of vitrinites in coals during coking process has effect on the properties of the coke. The evaluation of the vitrinites interaction is of great significance of coal blending and coke quality prediction. Vitrinites separated from the similar middle-rank coals in Tangshan (TS) and Ewirgol (EW) are mixed with ratio of 0:1, 1:3, 1:1, 3:1, 1:0 to prepare cokes. The characteristics of coke-CO2 gasification were studied to evaluate the interaction of vitrinites during coking process. The results show that the maximum reaction rate (rmax) and the comprehensive gasification index (Gc) of cokes have negative quadratic linear relationships with the content of TS vitrinite, and the difference between the experimental and theoretical gasification reactivity of cokes indicates the interaction of EW and TS vitrinites in the coking process. An interaction index (δ) based on the gasification reactivity of cokes is proposed to characterize the degree of interaction between the two kinds of vitrinites in coking process, and the interaction index based on Gc is 6.9%. Also, XRD and Raman spectroscopy analysis results show that the microcrystalline structure parameters (n and fa) have a negative linear relationship with Gc, and the Raman parameter AD1+D2+D3+D4/AG has a positive quadratic linear relationship with Gc, the Raman parameter AG/AAll has a negative quadratic linear relationship with Gc. TS vitrinite in coal blending can enhance the graphite characteristics in the coke and increase the order degree of carbon structure in the coke, which improve the resistance of CO2 erosion for the cokes.