Creating high‐pressure environments is an indispensable method to explore structural change, stability, and the upper limits for the application of xylitol under extreme conditions. Herein, we report a detailed description of the vibrations and phase transition of xylitol under high pressures by Raman spectroscopy. We found a novel phase transition of xylitol under 8.07 GPa by changing the O–H and CH2 vibrations. As the pressure further increased, xylitol underwent an amorphous transformation at 16.94 GPa. This study opens a new research perspective for polyols and expands the application of xylitol under extreme conditions.