In this work, a mechanistic study of silver-catalyzed oxidative aminofluorination of alkynyl-imine has been carried out. Kinetic data support a reaction pathway involving fast amination of alkyne to mesoionic carbene silver complexes (MIC)nAg(I) (n = 1 or 2). The rate-determining step of the reaction is the fluorination of the Ag species supported by a single MIC.