A procedure was proposed for the synthesis of 7-trifluoromethylazolo[1,5-a] pyrimidines by reactions of 2-ethoxyvinyl trifluoromethyl ketones and 2,2-diethoxyvinyl trifluoromethyl ketone with 5(3)-aminoazoles. The reactions occurred under mild conditions, and the products were formed with high yield and regioselectivity. © 2009 Pleiades Publishing, Ltd.