A new series of reagents, N-phenyl-2-furylacrylohydroxamic acid and its eight analogues, together with eight pyridylazo reagents, were explored for the selective extraction and sensitive spectrophotometric determination of bismuth (III) in standard alloys and environmental matrices. Bismuth was first extracted with a hydroxamic acid into chloroform and a pyridylazo reagent was added to the extract to form an intensely coloured ternary complex for spectrophotometric analysis. The combination of N-p-methoxyphenyl-2-furylacrylohydroxamic acid (MFHA) and 5-iodo-5-(dimethylamino)-2-(2-pyridylazo) phenol (IDEPAP) provided the maximum selectivity and sensitivity (ϵ=6.5 × 1041 mol−1cm−1at 590 nm). The enrichment attained through solvent extraction together with the intense colour of the ternary complex enabled analysis of bismuth at levels of 1ppb (0.001 ppm) and lower.