The conversion of nitrogen in char (char-N) to NO was studied both experimentally and computationally. In the experiments, pulverized coal char was produced from a U.S. high-volatile bituminous coal and burned in a dilute suspension at 1170 K, 1370 K and 1570 K, at an excess oxygen concentration of 8% (dry), with different levels of background NO. In some experiments, hydrogen bromide (HBr) was added to the vitiated air as a tool to alter the concentration of gas-phase radicals. During char combustion, low NO concentration and high temperature promoted the conversion of char-N to NO. HBr addition altered NO production in a way that depended on temperature. At 1170 K the presence of HBr increased NO production by 80%, whereas the addition of HBr decreased NO production at higher temperatures by 20%. To explain these results, three mechanistic descriptions of char-N evolution during combustion were evaluated with computational models that simulated (a) homogeneous chemistry in a plug-flow reactor with entrained particle combustion, and (b) homogeneous chemistry in the boundary layer surrounding a reacting particle. The observed effect of HBr on NO production could only be captured by a chemical mechanism that considered significant release of HCN from the char particle. Release of HCN also explained changes in NO production with temperature and NO concentration. Thus, the combination of experiments and simulations suggests that HCN evolution from the char during pulverized coal combustion plays an essential role in net NO production. (C) 2008 The Combustion Institute. Published by Elsevier Inc. All rights reserved.