This research investigated the emission and evolution characteristics of fuel-N during the O-2/H2O combustion process of a typical bituminous coal (Shenhua). To avoid the catalytic interference of alkali metal salts, the demineralized coal obtained from the raw coal sample was employed for the investigation in this research. The effects of reaction temperature (T-r) and H2O concentration, which were two vital factors affecting coal combustion characteristics, on the emission characteristics of fuel-N during the combustion process were also taken into consideration. Isothermal combustion tests performed under different O-2/H2O conditions (Tr: 1073 and 1473 K; O-2: 30%; H2O: 0, 3.5, 8.5, 15, 20, and 30 vol %) indicated that relatively high concentrations of N2O, HCN, and NH3 were measured in the O-2/H2O combustion of the coal sample. With the increase of Tr and H2O concentration, more fuel-N would be released in the devolatilization/volatile oxidation stage of the reaction. The X-ray photoelectron spectroscopy results of chars after devolatilization indicated that most of the N-5 decomposed into HCN or converted to N-6 or N-Q in the early reaction stage at high temperatures and that N-Q was the dominated form of a nitrogen-containing functional group (C(N)) existing on the char particle surface. The reducibility of the chars after O-2/H2O devolatilization played vital roles in reducing the emission of NO during the whole O-2/H2O combustion process.