Static headspace gas chromatography-tandem mass spectrometry was used to identify volatile compounds from Senecio scandens Buch-Ham. The elemental composition of compounds was confirmed by exploiting the tandem mass spectra of isotopic peaks from the precursor ion. Some isomers were well distinguished by the diversified scan technologies of tandem mass spectrometry (MS/MS). The MS/MS included a product ion scan, a precursor ion scan and a neutral loss scan. The results showed that 46 volatile compounds were completely identified, and the great of majority compounds were α-pinene (11.93%), n-caproaldehyde (9.02%) and dehydrosabinene (6.22%). This qualitative method is convenient and accurate and can be considered as a complementary identification method for the qualitative analysis of volatile compounds in complex samples.