Abstract: Based on two herb residues-herbal tea waste (HTW) and penicillin mycelial waste (PMW), characteristics of NO_x precursors during their pyrolysis were investigated in a horizontal tubular reactor with the help of XPS and TGA technologies. Effects of thermal conditions and physicochemical properties of fuels were discussed and compared. The results demonstrate that protein-N is the main nitrogen form for both HTW and PMW, determining the dominance of NH₃ among NO_x precursors at any operational conditions. Thermal conditions would still change the ratio and total yield by intrinsically influencing their formation pathways. Subsequently, the effects could be sequenced as follows:high temperatures with rapid pyrolysis > high temperatures with slow pyrolysis > low temperatures with rapid pyrolysis ≈ low temperatures with slow pyrolysis. Moreover, at high temperatures with rapid pyrolysis, increase in particle size or decrease in moisture content would result in reduction of total yield by 5%-11% and 4%-6%, respectively. In addition, NH₃ yield is produced at low temperatures or slow pyrolysis with sequence of PMW > HTW and vice versa, depending on components in the fuels. Consequently, analyses on nitrogen forms in char and nitrogen distribution indicate that total yield of 20%-45% is observed to be independent of fuel type under typical pyrolysis conditions, which may provide helpful guidance for the clean reutilization of herb residues.