The solvent-free interaction of 1,2,4-triazine-5-carbonitriles with first synthesized 5-hydroxyethylsulfanyland 5-hydroxyethoxyethylsulfanyl-3-amino-1,2,4-triazoles at heating has been studied. It was shown that the presence of these substituents at the C5 position of 1,2,4-triazole changes the direction of the reaction, and 5-amino-1,2,4-triazines are formed as the main products, while the products of the ipso -substitution of the C5-cyano group containing the moiety of the substituted 1,2,4-triazole were isolated only as by-products. In the case of using 1,2,4-triazole with a fragment of monoethylene glycol at C5 position of triazine, the formation of a complex mixture of products occurred.