Four coal chars were prepared in a flat flame flow reactor (FFR), which can simulate the temperature and gas composition of a real pulverized coal combustion environment. The pore structure of chars was measured by mercury porosimetry and nitrogen adsorption, and the Hg and Brunauer-Emmett-Teller (BET) surface areas were obtained. The kinetics of NO-char was studied in a drop-tube furnace (DTF) and thermogravimetric analyzer (TGA). In the TGA experiments, the random pore model (RPM) was applied to describe the NO-char reactions and obtain the intrinsic kinetics. By presenting the data of DTF and TGA experiments on the same Arrhenius plot, it can be concluded that TGA is an available tool to study the kinetics of a high-temperature NO-char reaction. With respect to the DTF experiments, in comparison to the BET surface area, the Hg surface area is a better basis for normalizing the reactivity of different coal chars because of less scatter in the measured values, better agreement with TGA experimental data, and more stable values during the process of reaction. Moreover, by comparing the Hg surface area of chars before and after reactions, it is believed that the Hg surface area basis is more appropriate for high-rank coal chars. The determined kinetic rate constants are in good agreement with other data in the literature, and a new rate constant expression is proposed.