A sulfur-decorated perylene derivative, 1-propanethiol-N,N′-dicyclohexyl perylene-3,4,9,10 tetracarboxylic diimide (PTPDI), was synthesized and fully characterized by 1H NMR, 13C NMR, FTIR, HRMS, UV–vis absorption, fluorescence, fluorescence lifetime, fluorescence quantum yield, cyclic voltammetry, and thermogravimetric techniques. The optical, fluorescence, and scanning electron microscopies were employed to study its self-assembly process. The photophysical properties were affected strongly by modifying the propanethiol unit linking to the perylene core. Furthermore, the chromophore showed two irreversible oxidations and two quasi-reversible reductions in dichloromethane at modest potential. The optical properties of PTPDI in various conditions and complementary density functional theory calculations were reported. Due to steric hindrance of the bulky n-propyl mercaptan substituent, PTPDI molecules are arranged in slipped face-to-face fashion to form J-aggregates. Thus, the intermolecular π–π actions of the molecule are weak, causing its high luminescence efficiency. In the meantime, the space between perylene cores is very short (3.45 Å), which is favorable for the hopping transportation of charge carrier from one molecule to an adjacent one. PTPDI could be a candidate material for acquiring a well-defined organic nanostructure with excellent charge-transporting and light-emitting capabilities.