Gallium arsenide is used in semiconductor industries worldwide. Numerous waste etching solutions are produced during the processes of GaAs wafer production. Therefore, a complete and eco-friendly technology should be established to recover gallium as a gallium chloride solution and remove arsenic ion from waste GaAs etching solution. In this study, the gallium trichloride and arsenic trisulfide powders were dissolved in ammonia solutions to prepare the simulated solutions, and the pH value was adjusted to pH 2 by nitric acid. In the extraction step, the GaAs etching solutions were extracted using 0.5 M Cyanex 272 solutions in kerosene at pH 2 and 0.1 O/A ratio for 5 min. The extraction efficiency attained 77.4%, which had an optimal ratio of concentration, and the four steps extraction efficiency attained 99.5%. After extraction, iron sulfate heptahydrates were added into the raffinate, and the arsenic ions were precipitated. The removed rate attained 99.9% when the Fe/As ratio was 10. In the stripping step, the organic phase was stripped with 0.5 M hydrochloric acid at 1 O/A ratio for 3 min, and 97.5% gallium was stripped. Finally, the purity of gallium chloride solution was 99.95% and the gallium was seven times the concentration of the etching solutions.