A novel tetraphenylpyrene complex Py-DOAB was designed and synthesized using the ionic self-assembly strategy. Its luminescence property, phase structure, and gelation performance were then elucidated by corresponding experiments such as UV–visible absorption spectroscopy, photoluminescence spectroscopy, differential scanning calorimetry, and two-dimensional X-ray diffraction. Due to the steric effect of the substituted phenyl groups and peripheral alkyl chains, Py-DOAB can stack rotationally and self-assemble to form a helical supramolecular structure. As a consequence, the complex possesses a high quantum yield of luminescence both in solution (87%) and the solid state (69%). Moreover, with the guidance of a chiral molecule, the co-assembled gel system with a circularly polarized luminescence property can be constructed. Due to the high fluorescence quantum yield, in combination with the gelation ability and circularly polarized luminescence property of Py-DOAB, it is expected to be used for the manufacture of multifunctional luminescence devices.

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