Cyanex-925 in xylene was used for extraction and separation of antimony(III) and bismuth(III) from aqueous solution. It was found that Sb(III) gets quantitatively extracted in the range 0.1-0.8 M HC1 and 0.01-1.0 M H2SO4, while Bi(III) in the range 0.01-0.4 M HNO3. The extraction behaviour of both the metal ions was studied separately as a function of acid concentration, temperature, equilibrium time and stripping ability using various acids and bases. Based on these results, sequential methods for their separation from multicomponent mixtures were developed.