A headspace solid-phase microextraction (HS-SPME) method followed by gas chromatography-mass spectrometry (GC-MS) is described for the analysis of volatile compounds in the dry rhizome of Ligusticum chuanxiong Hort. Three types of SPME fibers including PDMS, PDMS-DVB and DVB-CAR-PDMS were investigated and the best extraction was achieved with the mixed fiber DVB-CAR-PDMS. Parameters for HS-SPME in terms of temperature and time, sample amount and particle size, and desorption time were also investigated. A polar capillary column was used for the chromatographic separation. As a result, 73 compounds were determined and identified by the HS-SPME-GC-MS method with at least 20 more compounds than those in the methods available. Comparison was made between HS-SPME-GC-MS and steam distillation (SD)-GC-MS methods. Using much less sample amount, shorter extraction time and simpler procedure, HS-SPME method can achieve similar results with those by SD. In conclusion, the present method is simple, rapid and effective and can be used for the analysis of volatile compounds in medicinal plants.