Abstract A new, efficient, catalyst-free, one-pot, three-component method for the synthesis of 2-amino-substituted 7-amino-1, 2, 4-triazolo [1, 5-a][1, 3, 5] triazines using 3, 5-diamino-1, 2, 4-triazoles, cyanamide, and triethyl orthoformate is developed. The reaction proceeds smoothly under microwave-assisted heating. Advantages of the method include using easily available reagents, short reaction times, and operational simplicity.