A combined synchrotron X-ray diffraction, Raman scattering, and infrared spectroscopy study of the pressure-induced changes in H3BO3 to 10 GPa revealed a new high-pressure phase transition between 1 and 2 GPa followed by chemical decomposition into cubic HBO2, ice-VI, and ice- VII at 2GPa. The layered triclinic structure of H3BO3 exhibits a highly anisotropic compression with maximum compression along the c direction, accompanied by a strong reduction of the interlayer spacing. The large volume variation and structural changes accompanying the decomposition suggest high activation energy. This yields a slow reaction kinetics at room temperature and a phase composition that is highly dependent on the specific pressure−time path followed by the sample. The combined results have been used to propose a mechanism for pressure-induced dehydration of H3BO3 that implies a proton disorder in the system.