The work aims to establish a method for the rapid determination of 4,4'-Dihydroxybiphenyl migration from polyphenylene sulfone milk bottles by surface-enhanced Raman spectroscopy (SERS) method based on Ag nanoparticles (AgNPs). The migration behavior of4,4′-dihydroxybiphenyl in polyphenylene sulfone milk bottles was studied through GB 31604.1-2015 and GB 5009.156-2016 and the obtained solution was filtered by a 0.22 μm filter membrane, and mixed with AgNPs to perform SERS test. Then, the results were validated by high performance liquid chromatography (HPLC). The AgNPs prepared in this study showeduniform distribution of stable points and good reproducibility, and the lowest detectable concentration of 4,4′-dihydroxybiphenyl could reach 1 mg/L. The intensity of the characteristic peak (1 278 cm−1) of 4,4′-dihydroxybiphenyl showed a good linear relationship with the mass concentration of 4,4-biphenyldiol in the range of 1-50 mg/L, and the correlation coefficient was 0.990 4. The recovery of 4,4′-dihydroxybiphenyl in milk bottles was 88.6%-92.8% with the relative deviations of 4.02%-6.50%, which was in good agreement with the HPLC. This method is rapid, accurate and user-friendly, and provides a technical reference for the determination of 4,4′-dihydroxybiphenyl in food contact materials and products.