Using the technology of gas chromatography-mass spectrometry, the qualitative and quantitative researches were conducted to analyze the harmful residue ingredients in the original film, the surface of OPP, OPP/INK after printing, the surface layer and barrier layer composite material of OPP/INK/AD/OPP/VMPET, finished product membrane of INK/AD/VMPET/AD/CPP. The results showed that in the three sample preparation methods of solid phase microextraction, ultrasonic extraction and Soxhlet extraction, ultrasonic extraction method could be used for both of qualitative and quantitative analysis, while solid phase microextraction could be used for qualitative analysis of finished films, therefore, ultrasonic extraction was chosen for sample pretreatment; the extraction efficiency of four kinds of extraction solvent to phthalic acid glycol ester was methylene chloride > n-hexane/ethyl acetate > acetone > methanol. The influence of storage time is great on butyl acetate with residue on the surface of base material, less on plasticizer phthalic acid glycol ester, but great on harmful residues of the surface , interlayer and finished products. Most of phthalic acid glycol ester mainly came from added chemical agents and adhesives in OPP/INK/AD/VMPET in dry compound process, while butyl acetate were mainly from the organic solvent ink in the printing process. The residue of phthalic acid glycol ester in the finished film was 38.74 mg/kg, and the residue of butyl acetate was 20.54 mg/kg.