This experiment aimed to study the migration of organic volatile compounds from different paper-based packaging materials into food simulants. The method was established using direct headspace sampling-gas chromatography/ mass spectrometry (HS-GC/MS) for detecting the migration of 23 kinds of VOCs from paper packaging materials with modified polyphenylene oxide (MPPO) as food simulant. The linear correlation coefficients (R) were greater than 0.998, and the relative standard deviations (RSDs) were from 1.4% to 4.6% (n=7), with detection limits 0.03~0.60 mg/dm2 and recoveries 81.2%~110.2%. The method was simple, quick, sensitive and reproducible. The method was applied to analyze the 23 VOCs in two types of paper packaging materials, and can meet the requirements for the determination of the migration of 23 organic volatile compounds from paper packaging materials.