Herein, a cost-effective iron-catalyzed cascade annulation strategy of amidines that leverages readily available gem-difluoroalkenes as versatile C1 synthons is described. This innovative protocol enables the simultaneous formation of three C-N bonds and one C-O bond in a single catalytic system, delivering structurally diverse 2-aroyl-1,3,5-triazines with isolated yields up to 85%. The system exhibits broad functional group compatibility and efficient construction of triazine derivatives. Mechanistic studies suggest two plausible pathways are involved in this one-pot reaction.