An　efficient　transition　metal-free　annulation　of　amidine　with　ethyl　bromodifluoroacetate　to　access　2,4-disubstituted-1,3,5-triazines　is　firstly　presented.　The　desired　symmetric　and　unsymmetric　2,4-disubstituted-1,3,5-triazines　were　obtained　in　decent　yields　via　multiple　C-N　bond　formation,　in　which　ethyl　bromodifluoroacetate　is　harnessed　as　a　unique　C1　synthon　via　quadruple　cleavage.　This　reaction　is　transition　metal-free,　oxidant-free　and　simple　in　operation,　and　only　lowly　toxic　inorganic　wastes　are　generated.