Guanidinium benzilate (GBA) and benzylammonium benzilate (BABA) have been prepared from guanidinium carbonate and benzylamine/benzilic acid. GBA has interionic, intraionic, and intermolecular hydrogen bondings giving a three-dimensional supramolecular assembly. The carboxylate ion is present in the resonance form with C-O distances are of 1.242 and 1.246Å in GBA, whereas in non-resonance form with C-O distances of 1.262 and 1.245Å in BABA. In BABA, an inverted dimer with inter ionic hydrogen bonding exist as a dimer with supramolecular assembly due to intermolecular hydrogen bonding between the ion pairs. So the counter cation decides the resonance form of the carboxylate ion, hydrogen bonding network and the disposition of the phenyl rings in the benzilate and benzyl moiety. The IR, 1H NMR and 13C NMR spectral data have been interpreted using the crystal structure data and by the comparison between the two similar derivatives. Both the compounds exhibit the emission at 442 nm (Blue) and 547.2 nm (Green) on excitation. Chromaticity indicated excellent emission characteristics of both GBA and BABA which is necessary for OLED applications.