Abstract: HS-SPME-GC-MS (Headspace solid phase micro-extraction coupled with gas chromatography and mass spectrometry) technology was applied to isolate and further identify the aroma compounds of peanut oil under different temperatures during thermal treatment. As a result of totally 54 volatiles, which could be divided into 8 classes and mostly comprised of aldehydes, were determined. Relative Odor Activity Values (ROAVs) of aroma compounds, which could be calculated based on their thresholds from references, were regarded as the new original date set for further data processing by multivariate statistical methods. An entirely new method, which was capable to select those characteristic aroma components from complex samples, that was firstly proposed by a combination of PCA and CA analysis. Finally, according to this method, 20 key characteristic aroma compounds of peanut oil under different temperatures were successfully picked out.