Perfluoroalkyl-containing aza-tricycles have been prepared in one synthetic operation via an ambient light-promoted three-component reaction of β-oxo esters, perfluoroalkyl iodide and DBU. Intramolecular C-FO and double C-HF weak interactions and intermolecular C-HO and C-Hπ hydrogen bondings were observed partly due to the incorporation of the perfluoroalkyl group. The perfluoroalkylated non-planar aza-tricycles exhibit interesting room-temperature AIE fluorescence and acid-induced fluorescence enhancement characters.