Nanoheterogenous ultrathin films containing perfluorinated domains were prepared via the layer-by-layer (LbL) electrostatic self-assembly method. The films are constructed from the amphiphilic cationic copolymer with perfluorinated side chains and poly(sodium styrenesulfonate) (PSS). The LbL process was optimized by the application of sonication which allowed linear growth of the film. The resulting film exhibited micellar structure with isolated fluorocarbon hydrophobic domains. The remarkable features of the films were their switchable wettability and friction properties. The obtained water-processable films can find a number of potential applications, e.g., as smart and low friction coatings.