The substitutional solid solutions composed of group VA-VIA nonmetallic elements has attracted considerable scientific interest since they provide a pressure-induced route to search for novel types of solid solutions with potential applications. Yet, the pressure-induced solid solution phase is unprecedented in the sulfide family. In this paper, the structural behavior of antimony trisulfide, Sb2S3, has been investigated in order to testify whether or not it can also be driven into the substitutional solid solution phase by high pressures. The experiments were carried out by using a diamond anvil cell and angle dispersive synchrotron X-ray diffraction up to 50.2 GPa at room temperature. The experimental results indicate that Sb2S3 undergoes a series of phase transitions at 5.0, 12.6, 16.9, 21.3, and 28.2 GPa, and develops ultimately into an Sb-S substitutional solid solution, which adopts a body-centered cubic disordered structure. In this structure, the Sb and S atoms are distributed randomly on the bcc lattice sites with space group Im-3m. The structural behavior of Sb2S3 is tentatively assigned by comparison within the A2B3 (A = Sb, Bi; B = Se, Te, S) series under high pressures.