The development of a novel and reliable surface‐enhanced Raman scattering (SERS) substrate for the surface corrosion analysis of bronze relics is an attractive research topic in cultural relic protection. A high‐performance SERS substrate was developed in the current investigation using Ag/ZIF‐8/Polyacrylonitrile (Ag/ZIF‐8/PAN) nanofibers. Silver nanoparticles were grown in situ by zeolite imidazolate framework‐8 (ZIF‐8) nanoparticles, and the substrate was examined in the surface corrosion analysis of bronze relics. In situ, growth of silver nanoparticles was ensured by the porous structure and active centers on ZIF‐8, coated on PAN nanofibers. Simultaneously, the adsorption of harmful rust‐alkaline copper chloride was enhanced on the surface of bronze relics. The extensive metal network was perturbed by the deposits, which substantially increased the intensity of the Raman characteristic peaks of the test objects. The signal strength of alkaline copper chloride at 118 cm−1 on the bronze surface increased from 1094 to 20,790. The exceptional SERS performance of silver nanoparticles with sharp edges demonstrates that the synergistic effect of ZIF‐8 nanoparticles and PAN nanofibers offers a considerable number of Raman‐enhanced hot spots. These results indicate that MOF‐based nanostructures offer a novel approach to enhancing the morphology of silver nanoparticles and expanding their potential applications in the field of cultural relic protection.