Summary: Langmuir monolayers and organized molecular films of comb polymers containing different kinds of fluorocarbon side‐chains with various chain lengths and substituted atoms at the ω‐position were characterized by surface pressure‐area isotherms as well as Brewster angle microscopy on a water surface and by scanning probe microscopies (AFM and FFM) and the out‐of and in‐plane X‐ray diffractions on the solid substrates, respectively. When compared with monolayers of fluorinated amphiphilic vinyl monomers, those of the corresponding comb polymers were significantly stabilized. The nanostructures of these organized molecular films changed considerably with the film fabrication method used (such as mixed monolayers with hydrogenated amphiphiles) and the deposition conditions as well as with minor chemical modification of the fluorinated comb polymers with different hydrophilic esters and fluorocarbon side‐chains. The characteristic friction behavior for films built up of the fluorinated amphiphiles and comb polymers was found to depend strongly on the chemical constituents of the outermost layer of the film surface.
