The silver-ion-based supramolecular adducts bearing long alkyl chains were prepared by reaction of pyridazine and silver alkylsulfonates. The-liquid crystalline behavior of the adducts was studied by differential scanning calorimetry, polarizing microscopy, temperature-dependent IR, and temperature-dependent X-ray diffraction. Each of the adducts exhibits two rectangular columnar mesophases having P2/a symmetry and has a strong tendency of parallel alignment of the alkyl chains orientating toward the surface of the glass substrate.