Ascertaining the authenticity of the unrefined sesame oil presents an ongoing challenge. Here, the determination of 2-propenal was performed by headspace solid-phase microextraction (HS-SPME) under mild temperature coupled to gas chromatography with time-of-flight mass spectrometry, enabling the detection of adulteration of unrefined sesame oil with refined corn or soybean oil. Employing this coupled technique, 2-propenal was detected in all tested refined corn and soybean oils but not in any of the tested unrefined sesame oil samples. Using response surface methodology, the optimum extraction temperature, equilibrium time, and extraction time for the HS-SPME analysis of 2-propenal using carboxen/polydimethylsiloxane fiber were determined to be 55°C, 15 min, and 15 min, respectively, for refined corn oil and 55°C, 25 min, and 15 min, respectively, for refined soybean oil. Under these optimized conditions, the adulteration of unrefined sesame oil with refined corn or soybean oils (1–5%) was successfully detected. The detection and quantification limits of 2-propenal were found to be in the range of 0.008–0.010 and 0.023–0.031 µg mL−1, respectively. The overall results demonstrate the potential of this novel method for the authentication of unrefined sesame oil.