A variety of synthetic approaches to the formation of bismuth(III) thiolates has been explored and compared. BiPh₃ was treated with a series of thiols of varying pK_a and functionality (2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptopyrimidine, 2-mercapto-1-methylimidazole and thiosalicylic acid) in a 1:3 ratio under a variety of reaction conditions: with toluene or mesitylene under standard reflux conditions and under microwave irradiation, and solvent free with conventional and microwave heating. All reactions, except those with 2-mercapto-1-methylimidazole and thiosalicylic acid, yielded the tris-substitution product in good yield and high purity. Thiosalicylic acid gave the complex Bi₂L₃ in all reactions carried out in solvent and PhBiL when solvent free, both complexes containing the doubly deprotonated dianion (L = O₂CC₆H₄-2-S). Reactions carried out in the microwave reactor generally gave comparable yields to the conventional methods but in significantly shorter times. However, the solvent free microwave reactions of 2-mercaptobenzoxazole and 2-mercaptopyrimidine caused partial decomposition to give microcrystalline Bi₂S₃. The solvent free reactions conducted with conventional heating methods were highly effective in the formation of the bismuth thiolates. Reactions with 2-mercapto-1-methylimidazole were problematic in giving either no reaction products or mixtures of compounds displaying various degrees of substitution. Partial decomposition (2–7%) to the disulfide was observed for both the bismuth thiolates derived from 2-mercaptopyrimidine and thiosalicylic acid on storage of a solution over several weeks.