Changes in the volatile substances of Muscat grape after storage were detected using electronic nose and headspace solid phase micro-extraction/gas chromatography mass spectrometry (HS-SPME/GC–MS), and the shelf quality of grapes was evaluated to identify aroma components. After storage at 0 ℃ for 20 days, the grapes were stored on shelves at temperatures of 18~20 ℃, and 8~10 ℃, which simulated room temperature and supermarket grape sale conditions, respectively. Physicochemical, sensory, and nutritional indices within five-day shelf life were measured using the electronic nose and GC-MS. The electronic nose detection results showed that principal component analysis and linear discriminant analysis methods could effectively distinguish between samples with different shelf times. The results of GC-MS analysis with the peak area normalization method showed that the content and composition of volatile substances in Muscat grape changed during the shelf life. For the main characteristic aroma components, the content of (E)-2-hexenal, geraniol, citronellol, and nerol decreased; the contents of ethanol, hexanol, and acetic acid increased; and the total peak area decreased. The pattern of the changes was generally consistent with the results of physicochemical indices and electronic nose analysis. Therefore, electronic nose combined with GC-MS is feasible for determining the aroma quality of Muscat grape during its shelf life.