This study reports the transformation behavior of nitrogen during the co-hydrothermal carbonization of sewage sludge and model compounds (microcrystalline cellulose, starch, lignin, and xylan) of food waste at 220 °C, with a focus on the reaction routes between starch/xylan and NH4+. Most of the nitrogen in the raw sludge was transformed into organic-N (44.6%) and NH4+ (23.3%) in the aqueous product, and only 20.3% of nitrogen was retained in the hydrochar. The added model compounds could react with organic-N (i.e., amino acids and amines) and NH4+ in aqueous products through Maillard and Mannich reactions, generating heterocyclic-N (especially pyrrole-N) which further polymerizes to form nitrogen-containing polyaromatic hydrochar. This leads to an increase in the retention rate of nitrogen to 36.8-50.9%, especially upon the addition of starch and xylan. During the hydrothermal carbonization of starch/xylan in the NH4+ solution, the polymers are first hydrolyzed into monomers, followed by their further reaction with NH4+ to generate pyrrole-N and pyridine-N in aqueous products (especially xylan), and the pyrrole-N can then polymerize with aromatic clusters to form hydrochar-N. The results show that the model compounds of food waste substantially affect the nitrogen transformation pathways during hydrothermal carbonization, mainly because of the structures of their monomers. These findings can guide the production of sludge-based hydrochar with the targeted regulation of nitrogen content and species.