Supramolecular self-assembly of low molecular mass amphiphiles is of topical interest with the urge to achieve precise control over the formation of various self-aggregated structures. Particularly, fabrication of multifarious nanostructures from single molecular backbone would be highly advantageous for task specific applications of the self aggregates. To this end, the present study reports the solvent triggered evolution of hierarchical self-assembled structures of cholesterol based glucose appended amphiphiles and the pathway of structural transition. The amphiphiles formed bilayered vesicles in water and gels in different organic solvents. In DMSO-water solvent mixture, it showed gradual transition in the morphology of self-aggregates from vesicle-to-fiber and intermediate morphologies depending on the solvent compositions. Microscopic and spectroscopic investigations showed that morphological transformation took place through fusion, elongation and twisting of self-aggregates owing to the reorganization of the amphiphiles (H-type to J-type) in varied solvent polarity. Moreover, sheetlike molecular organization originating from hydrogen bonding and solvophobic interaction played a vital role in the formation of nanoribbons that led to the formation of gel fibril network. This study endows a new strategy to develop solvent induced multistructured self-aggregates from a single molecular scaffold, unraveling the route of forming hierarchical self-assembly.