To achieve excellent conductivity and hole transport capability of organic photoelectric functional materials, ordered long range arrangement of triarylamine functional units is achieved by using a su-pramolecular assembly method. A new compound N1,N3,N5-tris(3-((4-(bis(4-(dodecyloxy)phenyl)amino)phenyl)amino)propyl)benzene-1,3,5-trimethamide (H1) was thus synthesized. UV-Vis absorption and fluorescence spectra showed that H1 had self-assembly characteristics in the weak polar solvent n-heptane. The self-assembly morphology of H1 was observed by optical microscope and Scanning Electron Microscope (SEM), respectively. Further, quantum chemical calculations and electrochemical measurements were performed. The calculated results and measured HOMO level (-5.14 eV) and LUMO level (-1.80 eV) were matched with the energy levels of perovskite. The thermal decomposition temperature of H1 was found to be 445 °C. Thus, H1 could be potentially applied as a hole transport material in the perovskite solar cell.