Nano- and micrometer size spherical bismuth particles were prepared by reducing bismuth salts in simple and mixed polyols at elevated temperatures. In general, the conversion to metallic bismuth was preceded by the formation, at intermediate temperatures, of bismuth-polyol compounds. By changing the type of bismuth salt, the composition of the polyol mixture, and the temperature of the process, these precursors were successfully converted into spherical bismuth particles. It was found that the reduction process proceeds only if the temperature of the polyol exceeds the values at which the intermediate bismuth-polyol are stable, which was determined to be around 220 °C.