Group I−III−VI ternary chalcogenides have attracted extensive attention as important functional semiconductors. Among them, Cu−In−S compounds have seen strong research interest due to their potential applications in high-efficiency solar cells. However, the controllable synthesis of Cu−In−S nanostructures with different phases is always difficult. In this research, zincblende CuInS 2 , wurtzite CuInS 2 , and spinel CuIn 5 S 8 could be selectively synthesized using spinel In 3−x S 4 as the precursor by a simple solvothermal method. X-ray powder diffraction was used to determine the phase and crystal structure, and transmission electron microscopy was employed to characterize the morphologies of the as-prepared samples. Experiments showed that the acidity−basicity of the reaction system and the coordination and reducibility of the capping ligands were crucial to the final phases of the products. The UV−vis−NIR spectra of the three phases all exhibited a broad-band absorption over the entire visible light and extending into the near-infrared region, and the zinc-blende, wurtzite, and spinel Cu−In−S nanocrystals showed band gaps of 1.55, 1.54, and 1.51 eV, respectively, which indicates their potential applications in thin-film solar cells.