Ferrocenyl-substituted N-heterocyclic carbene (NHC) transition metal complexes have received considerable attention in recent years due to their extensive applications in homogenous catalysis or electro-chemical investigation. In this work, four NHC-silver complexes(NHC)(2)AgX(X = PF6 or BF4) were synthesized by the reactions of N-ferrocenylmethyl-N'-(pyridylmethyl) imidazolium salts with Ag2O under the phase transfer catalytic conditions, and were characterized by elemental analysis, NMR and single-crystal X-ray crystallographic analysis. The silver atom in four complexes showed a two-coordinated linear structure. The pyridyl nitrogen atom didn't take part in the coordination to the silver center. Those complexes exhibited highly effective catalytic activity in the three-component coupling reaction of aldehyde, alkyne and amine.