In order to investigate the effects of iron and calcium on the conversion pathway of nitrogen-containing substances in proline pyrolysis, this study conducted rapid pyrolysis experiments of proline with the addition of iron and calcium (Fe₂O₃, CaO and Fe₂O₃ + CaO) at different temperatures (300°C, 400°C, 500°C and 600°C), and combined with in situ infrared spectroscopy analysis. DKP was found to be formed in the first stage of proline pyrolysis by bimolecular dehydration condensation. The yield reaches 27.6%. Iron and calcium both promote the formation of pyrazine, pyrrole, pyridine and other monocyclic nitrogen-containing products, and iron changes the main pathway of pyrrole generation to dehydration followed by decarbonylation. When iron and calcium are added simultaneously, iron can extend the temperature interval of calcium-promoted purine generation to 500°C and synergistically make pyridine yield up to 21.3%.