<p>Cold-pressed grape seed oil provides a complex mixture of volatile organic compounds (VOCs) that contribute to its aroma and overall quality. However, the analysis of these compounds is challenging due to their wide range of individual boiling points and the limited sample volumes available because of the labor-intensive oil extraction process. This study aimed at evaluating and comparing three extraction techniques—multiple static headspace (MHS), dynamic headspace (DHS), and direct thermal desorption using slitted microvials (ATEX)—based on standard validation criteria, including repeatability and reproducibility, linearity, coefficient of determination, accuracy, and lower limit of quantification. Additionally, chromatographic performance was assessed by measuring signal intensity and the number of detectable peaks. Separation and detection were performed using gas chromatography-electron ionization-single quadrupole mass spectrometry (GC-EI-MS). Overall, DHS showed the best performance across the validation parameters for cold-pressed grape seed oil, while ATEX proved to be the most suitable option when only limited sample material is available, whereas MHS offered simplicity in handling. These findings indicate that DHS is a robust and versatile method for analyzing grape seed oil’s VOC, which is particularly suitable for untargeted screening and compound identification, and may also be applicable to other edible oils such as olive oil.</p> Graphical Abstract <p></p>