This paper describes the extraction behavior of Ga(III) along with associated metal ions, viz., V(V), Ge(IV), Ti(IV), V(IV), Tl(III), In(III), AI(III), Fe(III), Cd(II), Zn(II), Ni(II), and Mn(II), by bis(2,4,4-trimethylpentyl)dithiophosphinic acid (Cyanex 301) from different mineral acid media. The effect of different variables such as equilibration time, temperature, nature of diluent, and concentration of acid, metal ion, and extractant on the extraction of Ga(III) has been investigated. The extracting species has been identified. It has been possible to attain separations of Ga(III) from commonly associated metal ions by selective extraction/stripping. The partition behavior has been successfully extended to the recovery of gallium in good yield with high purity from Bayer's liquor. The commercial feasibility of the proposed procedure is supported by the fact that the extractant has good hydrolytic stability, regeneration power, and reasonable loading capacity.