A series of novel 4-(arylmethylidene)amino-5-(2-ethoxyphenyl)-3-mercapto-4H-1,2,4-triazoles (2a-f) were easily synthesized in high yields by means of the reactions of 3-(2-ethoxyphenyl)-4-amino-5-mercapto-4H-1,2,4-triazole (1) with various aromatic aldehydes. The compound, 4-(4-methylbenzylidene)-amino-5-(2-ethoxyphenyl)-3-mercapto-4H-1,2,4-triazole was investigated with X-ray crystallography.