Langmuir films of multifunctional, hydrophilic polyethers containing a hydrophobic cholesterol group (Ch) were studied by surface pressure-mean molecular area (pi-mmA) measurements and Brewster angle microscopy (BAM). The polyethers were either homopolymers or diblock copolymers of linear poly(glycerol) (/PG), linear poly(glyceryl glycidyl ether) (/PGG), linear poly(ethylene glycol) ((PEG), or hyperbranched poly(glycerol) (hbPG). Surface pressure measurements revealed that the homopolymers /PG and hbPG did not stay at the water surface after spreading and solvent evaporation, in contrast to /PEG. Because of the incorporation of the Ch group in the polymer structure. stable Langmuir films were formed by Ch-/PG(n), Ch-/PGG(n), and Ch-hbPG(n). The Ch-hbPG(n), Ch-/PEG(n), Ch-/PEG(n) -b-/PG(m), Ch-/PEG(n)-b-/PGG(m), and Ch-/PEG(n)-b-hbPG(n), systems showed an extended plateau region assigned to a phase transition involving the Ch groups. Typical hierarchically ordered morphologies of the LB films on hydrophilic substrates were observed for all Ch-initiated polymers. All LB films showed that Ch of the Ch-initiated homopolymers is able to crystallize. This strong tendency of self-aggregation then triggers further dewetting effects of the respective polyether entities. Fingerlike morphologies are observed for Ch-/PEG(69), since the /PEG(69) entity is able to undergo crystallization after transfer onto the silicon substrate.