The quality of oysters is reflected by volatile organic components. To rapidly assess the freshness level of oysters and elucidate the changes in flavor substances during storage, the volatile compounds of oysters stored at 4, 12, 20, and 28 °C over varying durations were analyzed using GC-MS and an electronic nose. Data from both GC-MS and electronic nose analyses revealed that alcohols, acids, and aldehydes are the primary contributors to the rancidity of oysters. Notably, the relative and absolute contents of Cis-2-(2-Pentenyl) furan and other heterocyclic compounds exhibited an upward trend. This observation suggests the potential for developing a simpler test for oyster freshness based on these compounds. Linear Discriminant Analysis (LDA) demonstrated superior performance compared to Principal Component Analysis (PCA) in differentiating oyster samples at various storage times. At 4 °C, the classification accuracy of the optimal support vector machine (SVM) and random forest (RF) models exceeded 90%. At 12 °C, 20 °C, and 28 °C, the classification accuracy of the best SVM and RF models surpassed 95%. Pearson correlation analysis of the concentrations of various volatile compounds and characteristic markers with the sensor response values indicated that the selected sensors were more aligned with the volatiles emitted by oysters. Consequently, the volatile compounds in oysters during storage can be predicted based on the response information from the sensors in the detection system. This study also demonstrates that the detection system serves as a viable alternative to GC-MS for evaluating oysters of varying freshness grades.