In situ angle dispersive synchrotron X-ray diffraction and Raman scattering measurements under pressure are employed to study the structural evolution of Cu4Bi4S9 nanoribbons, which are fabricated by using a facile solvothermal method. Both experiments show that a structural phase transition occurs near 14.5 GPa, and there is a pressure-induced reversible amorphization at about 25.6 GPa. The electrical transport property of a single Cu4Bi4S9 nanoribbon under different pressures is also investigated.