The manufacture of semiconductor materials containing gallium and indium requires the separation of these metals owing to their coexistence in the resources of these materials. In this work, solvent extraction of In(III) and Ga(III) from a hydrochloric acid solution by ionic liquids (ILs) was investigated to separate them. The ILs were synthesized by reacting organophosphorus acids (Cyanex 272, PC88A and D2EHPA) and Aliquat 336 (ALi-CY, ALi-PC, and ALi-D2). In(III) was selectively extracted over Ga(III) by the ILs in the range of initial pH from 0.1 to 2.0. The equilibrium pH was always higher than the initial pH because of the coextraction of hydrogen ions. The highest separation factor between In(III) and Ga(III) was 87, which was obtained by ALi-PC at an initial pH of 1.0. Stripping of the loaded ALi-PC with hydrochloric and sulfuric acid led to selective stripping of In(III) over Ga(III). Scrubbing of the loaded ALi-PC with pure In(III) solution was not effective in removing the small amount of Ga(III) present in the loaded ALi-PC. Batch simulation experiments for the three counter-current extraction stages indicated that the complete separation of both metal ions was possible by extracting In(III) using ALi-PC, with remaining Ga(III) in the raffinate.