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As of supramolecular assemblies are ultimately inscribed in their nanostructures, strategies that can precisely fabricate and regulate supramolecular architectures from small molecules are of great importance. Herein, in this research multiple modulations of supramolecular assembled structures of a natural triterpenoid-tailored bipyridinium amphiphile, 1-[2-(methyl glycyrrhetate)-2-oxoethyl]-[4,4']bipyridinium bromide (MGBP), have been achieved by adjusting solvents or counterions. Depending on the polarity of solvents, MGBP assembled i