Olibanum is a resinous traditional Chinese medicine that is directly used as a powder. It is widely used in China and is often combined with other traditional Chinese medicine powders to promote blood circulation and relieve pain, as well as to treat rheumatism, rheumatoid arthritis, and osteoarthritis. Powdered traditional Chinese medicine is often easily contaminated by microorganisms and 60Co irradiation is one of the good sterilization methods. Volatile organic compounds (VOCs) are the main active ingredient of olibanum. The aim of this study was to validate the optimum doses of 60Co irradiation and its effect on VOCs. 60Co irradiation was applied in different doses of 0 kGy, 1.5 kGy, 3.0 kGy, and 6.0 kGy. Changes in VOCs were detected using gas chromatography ion mobility spectrometry. A total of 81 VOCs were identified. The odor fingerprint results showed that, with an increase in irradiation dose, most of the VOCs of olibanum changed. Through principal component analysis, cluster analysis, and partial least squares discriminant analysis, it was demonstrated that, at 1.5 kGy, the impact of radiation on the VOCs of olibanum was minimal, indicating this is a relatively good irradiation dose. This study provides a theoretical basis for the irradiation processing and quality control of resinous medicinal materials such as olibanum and it also provides a good reference for irradiation technology development and its application to functional foods, thus making it both significant from a research perspective and useful from an application perspective.