The reaction of 5-hydroxymethylfurfural (HMF) with serine, threonine, gamma-aminobutyric acid and alanine, and the relative volatile substances were determined by Gas Chromatography-Mass Spectrometer (GC-MS). The results showed that 21 volatile components in total were detected from the reaction system of HMF and these amino acids, most of which were carbonyl compounds, furans and hydrocarbon compounds. In HMF-Serine system, the concentrations of pyrazine，5-methyl-2-furaldehyde and nonanal were the highest in the reaction system with the highest contents of the reactants and the longest reaction time. In HMF-Threonine system, the production of acetophenone, 3-methyl-pyrazine and 2,5-dimethyl-pyrazine was positively influenced by the reaction time. However, the reactants concentration had no significant effect on their production. In the HMF-aminobutyric acid system, the production of decanal increased as the reaction time prolonged, and the reactant concentration has significant effect under long-time reaction condition. In HMF-Alanine system, the production of nonanal and decanal increased as the reaction time prolonged, while decreased as the initial reactant concentration increased.