An artificial peptide, N-3-GVGV-OMe (G, glycine; V, valine), which mimics the repeating GAGA (A, alanine) sequence in Bombix Mori silk, was synthesised via solution-phase synthesis. Compared with N-3-GAGA-OMe sequence, N-3-GVGV-OMe showed high solubility in common organic solvents (such as CHCl3, THF and CH2Cl2), and easily formed organogels simply by adding poor solvents (such as toluene or ether) to the peptide solution at room temperature. The hierarchical nanostructure of N-3-GVGV-OMe organogel was dependent on the nature of the poor solvents, although in all cases, -sheets were formed exclusively. Gels formed in ether showed higher level hierarchical assembly, as evidenced by AFM and CD studies. Solution-state FT-IR analysis showed that the pre-organisation of the peptides in solution was not significant, and well-defined antiparallel -sheets were formed after the addition of the poor solvent. The high solubility and strong tendency for self-assembly of N-3-GVGV-OMe, together with its terminal azide group, might facilitate the modification of functional organic molecules even macromolecules for better nanostructure control.