A transition metal-free and external oxidant-free annulation of substrates having two nitrogen-nucleophilic sites with ClCF₂COONa was demonstrated, affording a series of 1,3,5-triazines and quinazolinones in up to 96% yields. Notably, ClCF₂COONa was employed as the C1 synthon for valuable heterocycles. Using this protocol, two C–N bonds were formed in one pot via the cleavage of two C–F bonds, one C–Cl bond and one C–C bond. This method avoided the use of a transition metal and an oxidant and generated low toxicity inorganic waste.