The reaction of the promesogenic dihexadecyl-2,2¢-bipyridine-4,4¢-dicarboxylate (L16) with a number of AgX salts produces a series of silver(I) complexes [(L16)Ag(sac)], 1, [(L16)Ag(NO3)], 2, [(L16)Ag(OTf)], 3, and [(L16)3Ag2](ClO4)2, 4, whose stoichiometries, molecular architectures, supramolecular networks and mesomorphic behaviour are “anion dependent”. In spite of the large differences in the single molecular structure, the one-dimensional coordination networks involving the triflate and perchlorate in complexes 3 and 4, are the key element for inducing significant argentophilic intermolecular interactions responsible for the induction of lamello-columnar mesomorphism in both Ag(I) derivatives. Moreover, a series of Ag(I) triflate model complexes have been synthesized and in order to get more insights about their solid state architectures, systematic structural studies have been performed.