Five Chinese coal chars were prepared in a flat flame flow reactor that can simulate the conditions of real pulverized coal combustion. The kinetics of the NO-char reaction at 1273, 1373, 1473, and 1573 K was studied in a drop tube furnace. A new model of the high-temperature NO-char reaction that took into account the pore diffusion and thermal annealing of char was proposed. The NO-char reaction was predicted by a combination of the model and computational fluid dynamics. Through the comparison of experimental and predicted results, the kinetic parameters for all chars were determined. The predicted results agree well with experimental results at 1273, 1373, and 1473 K, but the model largely underestimates the experimental data at 1573 K. This behavior is explained by a new mechanism of the high-temperature NO-char reaction. In addition, the model successfully normalizes the reactivity of chars with different ranks at high temperature, which is considered to be valuable in predicting the NO reduction on char surface at high temperature.