Only a minor part of Maillard reaction studies in literature focused on the reaction between carbohydrates and peptides. Therefore, in continuation of a previous study in which the influence of the peptide C-terminal amino acid was investigated, this study focused on the influence of the peptide N-terminal amino acid on the production of pyrazines in model reactions of glucose, methylglyoxal, or glyoxal. Nine different dipeptides and three tripeptides were selected. It was shown that the structure of the N-terminal amino acid is determinative for the overall pyrazine production. Especially the production of 2,5(6)-dimethylpyrazine and trimethylpyrazine was low in case of proline, valine, or leucine at the N-terminus, while it was very high for glycine, alanine, or serine. In contrast to the alkyl substituted pyrazines, unsubstituted pyrazine was always produced more in case of experiments with free amino acids. It is clear that different mechanisms must be responsible for this observation. This study clearly illustrates the capability of peptides to produce flavor compounds like pyrazines.