Developing new methods for synthesizing compounds incorporating both Imidazo[1,2- a]pyridines and fluoro fragments is a required technology. Herein, an expedient [3 + 3] annulation method to synthesize ring-fluorinated imidazo[1,2- a]pyridines via two consecutive C-F substitutions from readily available 1C,3N-dinucleophiles and β-CF 3-1,3-enynes is described. This protocol shows several attractive characteristics, such as readily available and inexpensive substrates, a broad range of functional groups, step and atom economy, and mild reaction conditions without any transition-metal catalysts.