The hydrothermal gasification of xylose, as a model substance of hemicellulose, was carried out at high temperatures and pressures (up to 400 °C, 25 MPa) in the presence of acetic acid by using continuous-flow reactor. As acetic acid is one kind of organic compound, environmental friendly, low corrosiveness, and also byproduct of hemicellulose gasification, it was chosen to be the catalyst to understand more about the behavior of each reaction in supercritical gasification of xylose. This study aimed to compare the reaction rate constant of xylose decomposition with and without acetic acid addition. The experiments were investigated to determine the influence of residence time varied from 0.5 to 5 s. The concentration of xylose was 1.5 wt% mixed with 1.5 wt% of acetic acid. When acetic acid was added in supercritical gasification of xylose, it acted as radical scavenger and provided H+, so the retro-aldol reaction and carbon gasification production, which are radical reactions, were be suppressed. Meanwhile, the dehydration of xylose and xylulose to furfural was be promoted significantly.