Taking the single-material polyethylene (PE) composite film used for food packaging as the object, the volatile compounds migrating from PE films into 95% ethanol food simulants were analyzed using direct immersion-solid phase microextraction-gas chromatography-mass spectrometry (DI-SPME-GC-MS) technology for non-targeted screening and quantitative analysis. Safety assessment was performed based on specific migration limits and threshold of toxicological concern (TTC) according to food safety standards. The results showed that GC-MS analysis identified 22 volatile migrants, predominantly alkanes and benzene-containing compounds, with low migration concentrations. Most compounds were classified as Cramer Class I low-toxicity substances. The safety evaluation demonstrated that all detected migrants exhibited TTC values significantly below safety thresholds, indicating no potential health risks. The results confirm that volatile substances released from PE composite films under normal usage conditions comply with food safety standards and pose negligible health concerns.