The synthesis of 1,2,3-triazoles with sulfur-based side chain has been accessed with the metal-free annulation reactions of readily available β-thiolated enaminones and tosyl hydrazine. By these reactions with water as the only medium, a broad array of 5-thiolated 1,2,3-triazoles have been synthesized with generally good to excellent yields. Except using TMEDA (N,N,N',N'-tetramethylethylenediamine) as the only base promoter, not any other catalyst or additive is required, thus providing an efficient and environmentally benign methods for useful 1,2,3-triazole synthesis.