The invention belongs to the multilayered thin film preparation field; it concretely involves a method that uses the ion peel-off technology to prepare large area layered assembly self-support membrane, including basis processing, layered-assembly membrane preparation, configuration of the peeling solution, preparation layered assembly self-support membrane using ion peel-off technology. The invention is not limited by the basis size, the shape, the type, and always holds true in the plane, the bended surface and the anomalous surface's, it can make the self-support membrane which are tubular or more complex form. This has a vital significance: On one hand, self-support membrane helps to research the layered assembly film's performance expediently, opens out the inner contact between the layered assembly film's performance, the chemical composition of the film and microscopic structure. On the other hand, compared with the layered assembly film which adheres to the solid fundus, self-support membrane will expand the application of the layered assembly film, including separating the membrane, the sensor, the catalyzed function thin film, the micro mechanism, even the man-made apparatus.