Inthis work, we describe self-assembled surfaces with a peculiarmultiscale organization, from the nanoscale to the microscale, exhibitingthe Cassie–Baxter wetting regime with extremely low water adhesion:floating drops regime with roll-off angles < 5°. These surfacescomprise bundles of hierarchical, quasi-one-dimensional (1D) TiO2nanostructures functionalized with a fluorinated molecule(PFNA). While the hierarchical nanostructures are the result of agas-phase self-assembly process, their bundles are the result of thecapillary forces acting between them when the PFNA solvent evaporates.Nanometric features are found to influence the hydrophobic behaviorof the surface, which is enhanced by the micrometric structures upto the achievement of the superhydrophobic Cassie–Baxter state(contact angle (CA) ≫ 150°). Thanks to their high totaland diffuse transmittance and their self-cleaning properties, thesesurfaces could be interesting for several applications such as smartwindows and photovoltaics where light management and surface cleanlinessplay a crucial role. Moreover, the multiscale analysis performed inthis work contributes to the understanding of the basic mechanismsbehind extreme wetting behaviors. [ABSTRACT FROM AUTHOR]