A modular multicomponent reaction of readily available fluoroalkyl alkenes, amidines, ammonium carbonate, and water was developed for the facile construction of β-fluoroalkylated aminovinyl ketones, which provided chemists a novel access to value-added organofluorine compounds. The reaction proceeded regio-/stereoselectively under mild conditions and exhibited good functional group tolerance. Cheap, stable, and low-toxic inorganic salt (NH4)2CO3 was first found to act as both a nitrogen source and a carbonyl equivalent in the multi-bond-forming process.