Amphiphiles containing fluorinated segments tend to aggregate in the aqueous solution into structure of lower curvature than their hydrocarbon analogs due to their larger diameter. A benefit of supramolecular structures incorporating fluorine moieties is their high electron density, which can be viewed in cryo‐TEM with better contrast than their hydrogenated forms. A modular approach has been developed for the synthesis of a new family of nonionic branched amphiphiles consisting of oligoglycerol units (G2) as the hydrophilic part and a branched fluorinated (F27) hydrophobic part. The design of this hydrophobic moiety allows to achieve a higher fluorine density than the previously used straight‐chain perfluoroalkanes. Two different chemical approaches, amide, and triazole, are used to link the hydrophilic and hydrophobic segments. In addition, the aggregation behavior is investigated by dynamic light scattering (DLS) and cryo‐TEM. The measurements prove the formation of multivesicular (MVVs) and multilamellar (MLVs) vesicles as well as smaller unilamellar vesicles. Further, the cell viability test proves the low cell toxicity of these nanoarchitectures for potential biomedical applications.
