Bismuth (Bi) is classic semi-metal with a low carrier density, small carrier effective masses, very long mean free path and highly anisotropic Fermi surface. In this work, we present a technique for the synthesis of bismuth nanometer-sized particles using an inverse microemulsion method. To prevent air-oxidation in the characterization stage, poly(vinylpyrrolidone) was used as protecting agent. Our characterizations reveal that single rhombohedral phase of bismuth can be obtained with ultrafine particle with ∼20 nm in size by following this synthetic route. The optical absorption spectrum of the aqueous nanoparticle colloids shows an absorption band at ∼268 nm.