Storage time significantly influences the aroma quality of peanut oil. In this study, gas chromatography–mass spectrometry (GC-MS) and gas chromatography–ion migration spectrometry (GC-IMS) were used to analyze the volatile flavor compounds of hot-pressed peanut oil baked at two temperatures (140 °C and 160 °C, denoted as OPO and RPO, respectively) during storage. The two methods detected 80 and 76 volatile flavor compounds, respectively, and principal component analysis (PCA) revealed clear distinctions between OPO and RPO during the storage period. Ten key aroma compounds were identified based on relative odor activity value (ROAV) analysis, including 3-methylbutanal, hexanal, heptanal, octanal, benzeneacetaldehyde, 3-ethyl-2,5-dimethylpyrazine,2-ethyl-6-methylpyrazine, acetylpyrazine, 2-methoxy- 4-vinylphenol, and acetic acid. During storage, the degradation and transformation of flavor compounds were more pronounced in RPO than in OPO. Physicochemical analyses showed increased acid and peroxide values, concomitant with decreased vitamin E and phytosterol content. Notably, these parameters changed more slowly in OPO than in RPO, confirming that OPO maintained superior quality over time. Correlation analysis suggested that changes in the aldehyde and pyrazine contents are key indicators of flavor and quality evolution in peanut oil during storage. This study provides insights into how baking temperature and storage time affect peanut oil aroma, elucidating the mechanisms of flavor variation and offering a theoretical basis for optimizing the flavor and quality of hot-pressed peanut oil.