Graphene oxide (GO)-based composite nanostructures and nanomaterials with self-assembly structures and novel functions have received considerable interests. In this work, organogels with various nanostructures via functional cationic gemini amphiphilic compound-GO nanocomposites were designed and prepared. The gel formation properties of gemini-GO nanoconnposites in different used organic solvents can be adjustable by controlling the symmetry in molecular skeletons of amphiphiles. Longer substituent alkyl chains and symmetric structures in molecular skeletons helped to increase hydrophobic force and flexibility in self-assembly process. A possible and reasonable mechanism for symmetry factors on the self-assembling process and prepared nanocomposites are given. It is clearly shown that the present functional amphiphilic compound-GO self-assembling research work will give important clues for the conceived preparation of novel GO nanocomposites and nanostructures.