We reported two pressure-induced phase transitions of goethite up to similar to 35 GPa using a diamond anvil cell in conjunction with ac impendence spectroscopy, Raman spectra at room temperature. The first pressure-induced phase transition at similar to 7.0 GPa is manifested in noticeable changes in six Raman-active modes, two obvious splitting phenomena for the modes and the variations in the slope of conductivity. The second phase transition at similar to 20 GPa was characterized by an obviously drop in electrical conductivity and the noticeable changes in the Raman-active modes. The variations in activation energy with increasing pressure were also discussed to reveal the electrical properties of goethite at high pressure.