Ultrasound-assisted emulsification solidified floating organic drop microextraction was used for preconcentration of trace amounts of bismuth prior to its determination by flame atomic absorption spectrometry. The bismuth ions were extracted by an organic microdrop composed of 1-dodecanol containing the complexing agent dithizone. The method involves the transferring of the bismuth ion from the aqueous solution to the organic phase under mild conditions. It combines the advantages of simplicity of liquid-liquid microextraction with the quickness of the ultrasound technique. All crucial parameters affecting the analytical performance were studied. Under optimum conditions, the enhancement factor was determined to be 29. The detection limit and precision were obtained as 7.5 ng/mL and 1.03% (n = 9, 100 ng/mL), respectively. The accuracy of the developed method was evaluated by analyzing a certified reference material and was successfully applied for the analysis of water samples.