The preparation of bismuth nanosheets ablating a high purity Bi target immersed in water subjected to an ultrasound wave is reported. The effect of the laser fluence used for ablation on the size and shape of the nanostructures synthesized was investigated. The obtained results reveal the formation of nanosheets with square-like shape and sizes from approximately 140–543 nm. In comparison, experiments without the ultrasound field lead to the formation of quasi-spherical nanoparticles. The nanosheets were characterized by means of transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), UV–Vis and Raman spectroscopies. The bismuth nanosheets, as deposited, are highly crystalline, and depending on the preparation conditions, the α or β phases of Bi2O3 are obtained. UV–Vis measurements show the typical band absorption characteristic of bismuth with nanometric size. Raman spectra confirm the formation of Bi2O3 nanostructures.