The properties of the coal-derived char play crucial roles in coal conversion reactions and the formation of air pollutants. The nascent char is highly reactive due to the existence of numerous free radicals, active sites, and organic functional groups on its surface. Here, we showed that a combination of nuclear magnetic resonance spectroscopy (NMR) and X-ray photoelectron spectroscopy (XPS) techniques is an effective and precise way to characterize the occurrence, distribution, and evolution of organic functionalities in coal chars. Using these methods, we explored detailed information about chemical features of super-fine pulverized coal chars in different atmospheres, and we also discussed the influence of particle size on the evolutionary behavior of functionalities. Results indicate that, in both N-2 and CO2 atmospheres, the content of C-O species increases with the reduction in char particle sizes. This increment facilitates the heterogeneous reduction of NOx on char surfaces. The chemisorbed NO is susceptible to being incorporated into chars, and being transformed into pyridine-type nitrogen with the favor of adjacent oxygen containing groups. Moreover, the significant increment in oxygen-containing groups with the reduction of particle size is further confirmed through C-13 NMR analysis. It was shown that there is an excellent correlation between estimates derived from XPS and NMR for oxygen configuration. The findings from this work provide some new insights into NOx reduction mechanisms and shed light on the practical application of superfine pulverized coal in the future. (C) 2016 Elsevier Ltd. All rights reserved.