Organogels have a wide variety of applications in the fields of chemistry, electricity, biomedicine and environmental engineering, which call for robust strategies for designing and developing novel organogelators. Here, we reported a pentapeptide, ECAYF, which was capable of forming a self-healing ethanol gel exhibiting viscoelastic and solid-like properties. The ethanol gel of ECAYF was stable for at least several months, suggesting strong non-covalent interactions between ethanol and the peptide in the gel. In the ethanol gel, self-assembled peptide fibrils were found to immobilize the ethanol molecules for gelation. Results also suggested that the EAF-5 peptide adopted H-bonding beta-sheet secondary structures, which further assembled into fibrils. Meanwhile, the self-assembly of the ECAYF peptide in mixtures of differently fractioned ethanol and H2O was observed, which clearly indicated that ethanol promoted the assembly of ECAYF in the solutions. These findings are helpful in understanding the roles of organic solvents as well as the complicated interactions between the solvent and gelator molecules in gelation.