Near infrared spectroscopy (NIR) was used to rapidly and economically identify the authentication of olive oil. NIR coupled with clustering analysis (CA) could use to identify many kinds of edible oils. Results indicated that CA revealed an obvious difference between olive oil and other edible oils. Meanwhile, a slight difference between olive oil and other edible oils was observed in principal component analysis (PCA). In this paper, NIR method played a good role in discrimination, which offered a new approach to rapid identification of pure and adulterated olive oil.