A series of codendrimers constituted by the first five generations of poly(propylene imine) (PPI) ionically substituted with 2H,2H,3H,3H-perfluoroundecanoic acid (af) and undecanoic acid (ac) in a fixed ratio (1:3) (af:ac) have been synthesized and their supramolecular organization has been investigated both in the liquid crystalline state and on a surface. Incompatibility generated by combining fluorinated and perhydrogenated chains in the same molecule causes a peculiar mesomorphic behavior depending on the generation of the codendrimers. Thus smectic A, frustrated smectic A or rectangular columnar mesophases have been detected. Despite their different liquid crystalline organization, they are capable to self-assemble in homogeneous molecular length layers on a surface, namely mica as revealed by atomic force microscopy (AFM) experiments. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 278-285, 2011