Abstract Nanocrystalline Bi2S3 particles have been synthesized from Bi and S powders by high-energy milling in a planetary mill. Structural and microstructural characterization of the prepared particles, including phase identification, specific surface area measurement and particle size analysis has been carried out. The optical properties were measured by spectroscopic methods and the structural stability up to 500°C was studied by thermal analysis. The production of orthorhombic Bi2S3 with crystallite size of about 26nm was confirmed by X-ray diffraction. The nanocrystals tend to agglomerate due to their large specific surface area. Accordingly, the average hydrodynamic diameter of the mechanochemically synthesized particles is 198nm. EDS analysis shows that the synthesized material is pure Bi2S3. The band gap of the Bi2S3 nanoparticles is 4.5eV which is wider than that in bulk materials. The nanoparticles exhibit good luminescent properties with a peak centered at 490 and 390nm. Differential scanning calorimetry curves exhibit a broad exothermic peak between 200 and 300°C, suggesting recovery processes. This interpretation is supported by X-ray diffraction measurements that indicate a 10-fold increase of the crystallite size to about 230nm. The controlled mechanochemical synthesis of Bi2S3 nanoparticles at ambient temperature and atmospheric pressure remains a great challenge.