Abstract: Non-reciprocal optical transmission properties of micro-nanostructures have important applications in the fields of micro-nano optics, communications, and materials science. In this paper, the nonreciprocal reflective properties of a superlattice film based on Au@Ag core-shell nanoparticles are investigated. The superlattice film was prepared by the interfacial self-assembly method, and the nitric acid etching and secondary growth strategies were used to realize the modulation of the forward/reverse asymmetric reflection properties of the Au@Ag superlattice film. The nitric acid etching process was utilized to remove the silver shell layer in the experiments, and the difference between the forward and reverse reflectivity of the films was significantly enhanced by adjusting the etching time, in which the reflectivity difference of the 3-layer structure reached 19.7%. Subsequently, star-shaped gold nanocluster structures were prepared on the surface of the etched film by the secondary growth method to further disrupt the symmetry of the film, and the difference between the forward and backward reflectivity of the second-grown film was enhanced to 75.3%. The self-assembled films can reduce the cost of device preparation and can be used for the design of non-reciprocal functionalized micro- and nanophotonic devices.