An isocyanide-functionalized imidazole was obtained from 4-(1H-imidazol-1-yl)aniline by the Ugi method and subsequently transformed into the corresponding imidazolium salt by treatment with MeI. Coordination of the isocyanide residue allowed the synthesis of several transition metal complexes containing a peripheral imidazolium cation, which are suitable starting materials for the formation of mixed ligand isocyanide–NHC heterometallic complexes.