5-substituted-3-hydrosulfuryl-4-hydroxybenzmethyleneamino-1,2,4-triazole were synthesized by reaction of 5-substituted-3-hydrosulfuryl-4-amino-1,2,4-triazole and hydroxybenzaldehyde in the presence of p-toluenesulfonic acid under solvent-free conditions by grinding at room temperature, and then, the synthesized compounds were reduced to 5-substituted-3-hydrosulfuryl-4-hydroxybenzylamino-1,2,4-triazole , The structures of the products were characterized by IR，NMR and MS. The procedure offers several advantages including milder reaction conditions，easier work-up and higher yields, It is a novel synthesis method of 5-substituted-3-hydrosulfuryl-4-arylmethylamino-1,2,4-triazole.