The present study analyzed and compared the volatile compounds in fresh Angelica acutiloba roots, stems and leaves both qualitatively and quantitatively. The volatile compounds were isolated by either steam distillation (SD) or headspace-solid phase microextraction (HS-SPME). A total of 61 compounds were identified using gas chromatography/mass spectrometry (GC/MS). All 61 compounds were verified by SD, with 3n-butyl phthalide, gamma-terpinene, p-cymene and cis-beta-ocimene as the main compounds. Thirty-three compounds were verified by HS-SPME, with gamma-terpinene and p-cymene as the main compounds. The leaf samples contained the highest essential oil content. Compared with SD, HS-SPME sampling resulted in relatively higher amounts of highly volatile monoterpenes and lower amounts of less volatile compounds such as 3n-butyl phthalide. These findings demonstrate that A. acutiloba roots, stems and leaves have high 3n-butyl phthalide contents; thus, all parts of A. acutiloba may be used for further application and development.