Solvent extraction separation of antimony(III) and bismuth(III) was carried out from aqueous acidic solutions with Cyanex 302 in toluene. Quantitative extraction of antimony(III) was observed in the acidic range of 0.1-1.0 M H2SO4 and 0.1-2.0 M HCl with 8.5 x 10(-2) M Cyanex 302 in toluene, whereas that of bismuth(III) was observed in the acidic range of 0.01-0.1 M HNO3 and 0.01-0.1 M HCl with 1 x 10(-2) M Cyanex 302 in toluene. Antimony(III) from the organic phase was stripped with 8.5 M H2SO4 and determined spectrophotometrically by the iodide method at 425 nm. Bismuth(III) from the organic phase was stripped with 2 M HNO3 and determined spectrophotometrically by the thiourea method at 470 nm. The optimum extraction conditions were evaluated by a critical study of acidity, extractant concentration, period of equilibrium and effect of diluents. Separation of bismuth(III) and antimony(III) from one another in varying ratios of 1:1, 1:2, 1:4, 2:1 and 5:1 and multicomponent mixtures of commonly associated metals was found to be possible by this method. It was successfully applied for analysis of antimony and bismuth in real samples.