Difunctionalization of unsaturated bonds with fluorinating reagents has been regarded as an efficient route to vic-difunctional organic fluorides. Here we report a copper-catalyzed synthesis of alpha-fluoroimines from diarylacetylenes and N-fluorobenzenesulfonimide. Mechanistically, the reaction initiates from the generation of imidyl radical, which reacts with alkyne to give the product. The resulting alpha-fluoroimine can easily be transformed into other organic fluorides such as fluoroketone and fluoroamines.