A novel and efficient multicomponent cyclization of methyl ketones, cyanamides, and arylamines for the synthesizing 2,4-diamino-1,3,5-triazines via consecutive formation of four C–N bonds is reported. This multicomponent reaction is characterized by the employment of two molecules of cyanamide for double C(sp3)–H amination of methyl ketones, avoiding complicated prepreparation of substrates and expanding the substrate scope. Furthermore, this multicomponent cyclization strategy provides a new approach for generating diverse 2,4-diamino...