In this study, unique luminescent gels have been obtained from two components between amino acid functionalized perylene derivatives and 4,4'-bipyridyl units via hierarchical self-assembly. The luminescent gels have been investigated by means of ultraviolet spectra (UV), fluorescence spectra, Scanning Electron Microscopy (SEM) and Laser Scanning Confocal Microscopy (LSCM), which illustrate the strong fluorescence intensity of the gels. In order to further reveal the self-assembly driving forces, the two-dimensional (2D) self-assembly behaviours have been studied by scanning tunneling microscopy (STM) on a highly oriented pyrolytic graphite (HOPG) substrate at the solid-liquid interface, which indicates that the driving forces are attributed to the intermolecular hydrogen bonding and π-π stacking interactions. According to the interaction mode, these organogelators are found to rapidly transform from gels to solutions by adding triethylamine.