The first representatives of 4-amino-1,3-diarylimidazolium chlorides have been synthesized by heating chloroacetonitrile with N,Nʹ-diarylformamidines containing alkyl substituents at positions 2 and 6 of the N-aryl groups. The possibility of postfunctionalization of the obtained aminoimidazolium salts by acylation of the amino group was demonstrated, as well as their applicability as precursors of N-heterocyclic carbenes in the synthesis of Cu/NHC complexes after preliminary protection of the amino group.