We have revealed Sb2S3 to have two phase transitions and to undergo metallization using a diamond anvil cell at around 5.0, 15.0, and 34.0 GPa, respectively. These results were obtained on the basis of high-pressure Raman spectroscopy, temperature-dependent conductivity measurements, atomic force microscopy, high-resolution transmission electron microscopy, and first-principles calculations. The first phase transition at similar to 5.0 GPa is an isostructural phase transition, which is manifested in noticeable changes in five Raman-active modes and the slope of the conductivity because of a change in the electronic structure. The second pressure-induced phase transition was characterized by a discontinuous change in the slope of conductivity and a new low-intensity Raman mode at similar to 15.0 GPa. Furthermore, a semiconductor-to-metal transition was found at similar to 34.0 GPa, which was accompanied by irreversible metallization, and it could be attributed to the permanently plastic deformation of the interlayer spacing. This high-pressure behavior of Sb2S3 will help us to understand the universal crystal structure evolution and electrical characteristics for A(2)B(3)-type compounds, and to facilitate their application in electronic devices.