The commercial samples of 10 kinds of pepper oil were qualitatively analyzed of different oxidation degrees by electronic nose technology combined with principal component analysis (PCA), cluster analysis (CA), linear discriminant analysis (LDA) and discriminant factor analysis (DFA). A model of rapid discrimination of pepper oil with different oxidation degrees was established using PCA, CA, LDA and DFA, respectively. Then 40 groups of samples were tested by the models. The results were compared with GB peroxide values method. The correct recognition rates of CA, PCA, LDA and DFA were 95.0%, 97.5%, 100% % and 97.5%, respectively. The results showed that electronic nose technology was able to determine the oxidation degree of pepper oil, and LDA analysis was a better method.