Abstract This research news describes the construction of polymeric nanostructured composite film based on a variety of interactions, such as hydrophobic–hydrophilic effect, electrostatic interaction, hydrogen bonding, etc. The work focused on developing strategies to solve the basic problems in the area of ultrathin film research, such as stability, improving the interface quality, creating patterned interface, and techniques to construct nanolayered structure. With in-depth study of the relationship between the microscopic layered architecture and macroscopic function of supramolecular assemblies, it is anticipated that one could obtain miniature devices or machines of high efficiency through integration of the assembling process and device fabrication.