Bismuth(III) was quantitatively extracted from 0.1M HCl with 1x10(-4)M of hexaacetato calix(6)arene in toluene. It was stripped with 2 M nitric acid and determined from the aqueous phase spectrophotometrically at 470 nm as its complex with thiourea. The various parameters such as pH, reagent concentration, kind of diluents, stripping agents, effect of diverse ions were studied to ascertain optimum conditions for the quantitative extraction of bismuth. Bismuth was separated from thorium(IV), iron(III), manganese(II), chromium(III), lead(II), palladium(II) and thallium(III) in multicomponent mixtures. The method was extended for the analysis of bismuth in real samples.