The method of headspace coupled with comprehensive two-dimensional GC-time-of-flight MS (HS-GC × GC-TOF/MS) was applied to differentiate the volatile flavor compounds of three types of pure vegetable oils (sesame oils, peanut oils, and soybean oils) and two types of adulterated oils (sesame oils and peanut oils adulterated with soybean oils).Thirty common volatiles, 14 particular flavors and two particular flavors were identified from the three types of pure oils, from the sesame oils, and from the soybean oils, respectively.Thirty-one potential markers (variables), which are crucial to the forming of different vegetable oil flavors, were selected from volatiles in different pure and adulterated oils, and they were analyzed using the principal component analysis (PCA) and cluster analysis (CA) approaches.The samples of three types of pure vegetable oil were completely classified using the PCA and CA.In addition, minimum adulteration levels of 5% and 10% can be differentiated in the adulteration of peanut oils and sesame oils with soybean oils, respectively.