The volatiles of Bulbus Allii Macrostemonis from different areas and different original plants have been studied by headspace combined with surface- enhanced Raman scattering (SERS) using nano- silver colloid as substrate. Volatile SERS spectra of Allium macrostemon Bunge from four different areas and Allium chinense from Chuxiong are very similar and well repeated. The peaks at 375, 635, 673, 712, 781, 893, 1025, 1086, 1222, 1322, 1629 cm-1 in their volatile SERS spectra match well with each other. The volatile SERS spectra are compared respectively with the volatile SERS spectra of liquid allyl methyl sulfide, 1- propanethiol and their mixture. The results show that the volatile SERS spectra of Allium macrostemon Bunge and Allium chinense are basically consistent with that of the mixture of liquid allyl methyl sulfide and 1- propanethiol. It illustrates that volatiles of Allium macrostemon Bunge from different areas and Allium chinense from Chuxiong contain allyl methyl sulfide and 1- propanethiol. All results have revealed that the headspace combining with SERS technology can be directly used to study volatiles of Bulbus Allii Macrostemonis.