The effects of enzymes like alcalase, papain and trypsin generates protein hydrolysates (PH-Ala, PH-Pap and PH-Tryp, respectively) from protein fraction (PF) of corn distillers solubles, were evaluated nitrogenous pyrolysate compounds (PyCs). The differences in absorbance values of amides (I, II, II, A, and B) were distinct to type of enzymatic treatments to PF. The nitrogenous PyCs comprised approximately 12, 21, 16, and 23% from fast pyrolysis of PF, PH-Ala, PH-Pap and PH-Tryp, respectively. Protein hydrolysates from enzyme treatment (PH-Ala, PH-Pap, and PH-Tryp) accumulated N-heterocyclics, amines & amides, and nitriles (10.78 ± 0.72, 8.29 ± 0.30, 9.66 ± 0.83) as the most abundant component and their profiles are further disclosed for these three classes as hexahydro-3-(phenylmethyl) pyrrolo [1,2 a] pyrazine-1,4-dione from PF, PH-Ala, PH-Tryp; bis(2-ethylhexyl) amine, n-butylidenebutylamine, N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, 6-acetamido-n-(5-cyanopentyl) hexanamide from PH-Ala, PH-Pap, PH-Tryp; and phenylacetonitrile & derivatives, phenyl isocyanate from PF, PHs, respectively. The diketopiperazines (DKPs) such as cyclo (Pro-Gly) and cyclo (Phe-Pro) were denoted with area% of 2.43, 7.55, and 4.72 from respective PF, PH-Ala, and PH-Tryp. The out-of-plane and in-plane bending of aromatic CH linkage, NO stretch, NH bend, CO stretch, CN stretch, and saturated aliphatic CH stretch marked nitrogenous PyCs. The findings suggest indicator molecules with monitor of hydrolytic pathways for future value-addition to PF.