Step pyrolysis of N-rich industrial biowastes was used to explore decisive reaction pathways and regulatory mechanisms of NOx precursor formation. Three typical ones involving medium-density fiberboard waste (MFW), penicillin mycelia waste (PMW) and sewage sludge (SS) were employed to compare the formation characteristics of NOx precursors during one-step and two-step pyrolysis. Results demonstrated that considerable NH3-N pre-dominated NOx precursors for one-step pyrolysis at low temperatures, depending on primary pyrolysis of labile amide-N/inorganic-N in fuels. Meanwhile, NOx precursors differed in the increment of each species yield while resembled in the total yield of 20-45 wt.% among three samples at high temperatures, due to specific prevailing reaction pathways linking with distinctive amide-N types. Subsequently, compared with one-step pyrolysis uniformly (800 degrees C), by manipulating intensities of reaction pathways at different stages (selecting differential intermediate feedstocks), two-step pyrolysis was capable of minimizing NOx precursor-N yield by 36-43% with a greater impact on HCN-N (75-85%) than NH3-N (9-37%), demonstrating its great capacity on regulating the formation of NOx precursors for industrial biowaste pyrolysis. These observations were beneficial to develop effective insights into N-pollution emission control during their thermal reutilization.