The work aims to set up a method that can determine 9 kinds of organic solvent residues in food baking paper packaging (butyl ketone, benzene, toluene, terephthalic acid, isophthalic acid, phthalic acid, ethyl acetate, butyl acetate ester, n-butyl alcohol). The headspace sample injector, chromatography and mass spectrometry of automatic headspace (HS)-gas chromatography (GC)-series triple level 4 pole mass spectrometry (MS/MS) were optimized for determination. The optimized conditions were as follows:the sample equilibrium temperature was 120 ℃, the headspace equilibrium time was 30 min, the compounds were separated by Thermo TG-WAXMS chromatographic column, and the injection flow ratio was 25∶1. The quantification was carried out by external standard method and the determination was conducted by GC-MS/MS of MRM mode. 9 kinds of organic solvents could be completely separated, with good linear correlation coefficients of above 0.99, method detection limit between 0.003 ~ 0.010 mg/m2, recovery rate between 93.8% ~ 101.5% and RSD between 1.3% ~ 3.5%. The method is easier and faster compared with gas chromatography, with good separation effect, accurate result and lower detection limit and can be used to actually determine 9 kinds of organic solvent residues in paper packaging products.