We disclose herein an efficient photochemical formal [3+2+1] annulation strategy for the transformation of diazocarbonyl compounds into various fluorinated nitrogen-containing heterocycles. This transformation is characterized by reacting fluoroalkyl radicals with α-diazoketones, which are used as infrequent denitrogenated synthons under visible light. Moreover, a wide range of N-heterocycles containing precious CF3 and perfluoroalkylated groups are constructed in moderate to good yields. Notably, this photochemical strategy may provide a fruitful path for the synthesis of complex organofluorides via diazo/fluorine/radical chemistry.