A new approach in synthesizing an open chain tetrabenzimidazolium salts as a precursor for the synthesis of dinuclear Ag(I) complex containing tetra-NHC (where NHC = N-heterocyclic carbene) is described. This tetrabenzimidazolium acylic carbene was prepared by alkyl and aromatic linker under aerobic condition. The novel tetra-NHC dinuclaer Ag(I) complex of the synthesized salt was obtained by in situ deprotonation using Ag2O. The structural studies of the complex revealed that the molecule exhibits as a dinuclear twisted structure with two Ag(I) ions coordinate linearly to the two pairs of carbenes. The pair of Ag(I) is further stabilised with the presence of argentophilic interaction.