Abstract The synthesis of 4-substituted-4H-1, 2, 4-triazole-3-thiols and 3-methylthio-4- substituted-4H-1, 2, 4-triazoles by the condensation of 4-substituted-3-thiosemicarbazides with dimethylformamide dimethyl acetal or dimethylacetamide dimethyl acetal is described. A discussion of the mechanistic pathway is included.