Background: Alpinia officinarum Hance is both an herbal medicine and a condiment, and generally has different cultivars such as Zhutou galangal and Fengwo galangal. The appearance of these A. officinarum cultivars is similar, but their chemical composition and quality are different. It is therefore important to discriminate between different A. officinarum plants to ensure the consistency of the efficacy of the medicine. Therefore, we used an electronic nose (E-nose) to explore the differences in odor information between the two cultivars for fast and robust discrimination. Methods: Odor and volatile components of all A. officinarum samples were detected by the E-nose and gas chromatography-mass spectrometry (GC-MS), respectively. The E-nose sensors and GC-MS data were analyzed respectively by principal component analysis (PCA), the correlation between E-nose sensors and GC-MS data were analyzed by partial least squares (PLS). Results: It was found that Zhutou galangal and Fengwo galangal can be discriminated by combining the E-nose with PCA, and the E-nose sensors S2, S6, S7, S9 were important sensors for distinguishing different cultivars of A. officinarum. A total of 56 volatile components of A. officinarum were identified by the GC-MS analysis, and the composition and content of the volatile components from the two different A. officinarum cultivars were different, in particular the relative contents of 1,8-cineole and α-farnesene. The classification result by PCA analysis based on GC-MS data was consistent with the E-nose results. The PLS analysis demonstrated that the volatile terpene, alcohol and ester components primarily interacted with the sensors S2 and S7, indicating that particular E-nose sensors were highly correlated with some aroma constituents. Conclusions: Combined with advanced chemometrics, the E-nose detection technology can discriminate two cultivars of A. officinarum, with GC-MS providing support to determine the material basis of the E-nose sensors’ response.