The buckling behavior of stiff/soft bilayer films has been extensively studied over the past three decades. However, strategies to characterize buckling structures on complex surfaces caused by bilayer film deformation, such as bending and spherical bilayers, are still lacking, preventing an accurate understanding of buckling behaviors in a broader context. Here, a frozen effect in a stiff/soft bilayer film is reported which provides a solution to the aforementioned problem. The buckling patterns in the stiff/soft bilayer film can be frozen by electron-beam irradiation, which is attributed to the irradiation-induced hardening transition of the soft film. After local freezing, the buckling patterns on a complex surface can be positioned on a plane by eliminating the compression across the bilayer and, hence, can be characterized by conventional means. This frozen characterization technique is similar to cryo-electron microscopy and has vast potential applications in many fields.