Abstract A new complex of melamine(MA) with benzoie acid(HBA) was prepared, affording [(HMA+)(BA−)]-2H2O. Each HBA molecule is deprotonated and one triazine nitrogen atom of MA is protonated. The adjacent HMA+ cations are related via an inverse center to form ribbons with a pair of N—H…N hydrogen bonds. COO− groups of BA− anions are hydrogen bonded to alternate sides of the (HMA+)∞ ribbons to generate indention 1D tapes, which are extended into a 3D structure via N—H…O− and N—H…OW hydrogen bonds and π…π stacking interactions. Predominant patterns of the hydrogen bond present in the complex are anion/water and amino/water tape structures. The hydrogen-bonding patterns consist of alternate 6, 10-membered rings sharing two edges. Infrared(IR) spectroscopy conforms that proton transfer has taken place in the complex.