The first synthesis of hexa(4-methylpyridylmethyl)benzene is described (as shown in scheme 1), which have been self-assembled with silver bromide (as shown in Fig. 1). This new cation has a high degree of symmetry, thus affording a very singular type of molecule; the formation of this type of supramolecule may open the door to the compounds with high-symmetry and peculiar properties. The supramolecule has been confirmed through single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, UV-vis diffuse reflectance spectra and TG. In addition, the fluorescence properties of compound in solid state was studied, which indicated that it could be employed as fluorescence sensors for detecting Fe3+ ions with high sensitivity and recyclability.