Six new Ag(I) coordination complexes, [Ag(abn)(4-cba)] 2 (1), [Ag(abn)(3-cba)] 2 (2), [Ag(abn)(fba)] 2 (3), [Ag(abn)(3-mba)] 2 (4), [Ag(abn)(moba)] 2 (5), [Ag(abn) 2 (4-mba)] n (6), (abn=2-aminobenzonitrile, 4-cbaH=4-chlorobenzoic acid, 3-cbaH=3-chlorobenzoic acid, Hfba=3-fluorobenzoic acid, 3-mbaH=3-methylbenzoic acid, Hmoba=2-methoxybenzoic acid and 4-mbaH=4-methylbenzoic acid), have been synthesized and characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. Complexes 1–4 are similar discrete binuclear Ag(I) motif containing monodentate μ 1 -N amino abn and μ 2 -η 1 :η 1 carboxylates. The complementary N amino –H⋯N cyano hydrogen bonds link the binuclear motifs into 1D chain which is further extended into 2D supramolecular sheet by N amino –H⋯O carboxyl hydrogen bonds. Notably, the electronic effect of substituents in 1–4 has deeply influence on the Ag⋯Ag interaction. Complex 5 is also a discrete binuclear Ag(I) motif but contains a monodentate μ 1 -N cyano abn ligand. The 1D chain was observed in complex 6 where two different abn ligands with μ 1 -N cyano and μ 2 -N cyano , N amino coordination modes coexist and 4-mba is a chelating μ 1 -η 1 :η 1 ligand. The results show that the different structures are predominantly attributed to the various ancillary carboxylate ligands and diverse coordination modes of abn ligand. Moreover, the emissive behaviors of them are discussed.