A non-destructive analysis method was established for the determination of volatile substances in folding cases using thermal desorption-gas chromatography/mass spectrometry. Tenax-TA tubes were used for the absorption and desorption of 10 target compounds. Under optimized chromatographic conditions, benzene, toluene, n-butyl acetate, ethylbenzene, m-xylene, p-xylene, styrene, o-xylene, n-undecane and furfural had good linear correlations. Samples in the laboratory were also obtained and analyzed. The results show that separation analysis of volatile hazardous substances can be achieved using this method.