Volatile components are one of the main active components of Ligusticum chuanxiong Hort and are important indicators for evaluating the medicinal quality of Ligusticum chuanxiong. To explore the effects of ⁶⁰Co-γ irradiation on the volatile components of Ligusticum chuanxiong,thesamples were treated with different irradiation doses, and the changes of the volatile components before and after irradiation were analyzed using an electronic nose combined with headspace solid-phase microextraction and gas chromatography-mass spectrometry. Principal component analysis (PCA), linear discriminant analysis (LDA), orthogonal partial least squares discriminant analysis (OPLS-DA), and cluster statistical analysis were used to elucidate changes in the volatile components of Ligusticum chuanxiongbefore and after irradiation. The electronic nose detection results and gas chromatography–mass spectrometry detection results indicated that ketone alkanes, alcohols, aldehydes, and ketones contributed to the odor of Ligusticum chuanxiong. Irradiation treatments at doses ≤10 kGy had no significant effect on the odor of Ligusticum chuanxiong. The results demonstrated that after irradiation at 0 kGy (control group), 3 kGy, 7 kGy, and 10 kGy, 60 compounds were identified in Ligusticum chuanxiong, including 23 hydrocarbons, 12 alcohols, 10 lipids, and 4 aldehydes or ketones, and 11 others. There were mainly 21 volatile substances that changed after irradiation, accounting for approximately 12.92% of the volatile components in Ligusticum chuanxiong; however, they were not the main volatile components of Ligusticum chuanxiong. No new compounds were identified in Ligusticum chuanxiongafter irradiation treatment within a dose of 10 kGy. The results provide a theoretical basis and reference for the influence of ⁶⁰Co-γ irradiation on the quality of Ligusticum chuanxiong samples and also lay a certain foundation for the application of irradiation in Ligusticum chuanxiong pieces and traditional Chinese medicine and simple preparation resources. The results indicate that the treatment of ⁶⁰Co-γ irradiation on the Ligusticum chuanxiong samples with doses ?10 kGy does not affect its main volatile components.