Solvothermal and hydrothermal methods have been employed to generate nano-sized Sb2S3 (stibnites) from a variety of xanthate, dithiocarbamate and dithiophosphate precursors. The solvothermal method allows control of morphology by regulating precursor and size by reaction time; this process also produces near-uniform and larger particles. The xanthate precursors are far superior to the dithiocarbamates in their ability to produce oxide-free Sb2S3. Aerosol-assisted chemical vapour deposition (AACVD) provided a means to produce good quality films of Sb2S3. The advantages of xanthate precursors is rationalised in terms of a facile, low-temperature Chugaev rearrangement.