The interaction between volatile and char is widespread in combustion. The effect of this interaction on the conversion of fuel-N to NO x is significant, but the mechanism remains to be comprehensively unveiled. Thus, in this paper, the NO and N 2 O conversion of nitrogen-containing biomass models (glutamate, glycine, phenylalanine) during combustion at high temperatures (800 - 1500 degrees C) is investigated using two combustion modes, separated combustion (in which volatile and char are burned separately) and coupled combustion (in which volatile and char are burned simultaneously), in an O 2 /Ar atmosphere. A new pathway for N 2 O formation resulting from the interaction between volatile and char is identified. At low temperatures, this interaction facilitates the conversion of fuel-N to N 2 O. For instance, during the separated combustion of glutamate at 800 degrees C, the conversion rates of fuel-N to N 2 O and NO are 26.3 % and 20.4 %, respectively. However, in coupled combustion, these conversion rates shift to 48.1 % for N 2 O and 3.6 % for NO. At high temperatures, this interaction promotes the conversion of fuel-N to NO. For instance, during the separated combustion and coupled combustion of glutamate at 1500 degrees C, the conversion rates of fuel-N to NO are 6.2 % and 16.6 %, respectively. Similar patterns are observed for the other two amino acids. In both combustion modes, the co-firing of cellulose, lignin, and hemicellulose with glutamic acid significantly suppresses the production of N 2 O. The conversion rate of N 2 O decreases by about 7 % - 10 %, while the impact on NO release shows either a suppressive or promotive effect in different temperature intervals. These results play a crucial role in the development of efficient and clean combustion technology for biomass.