The present article investigated the laser induced breakdown spectroscopy for a wide range of plastic (HDPE, LDPE, PET, NYLON) with the ultraviolet (UV) excitation wavelength. Compared with the National Institute of Standards and Technology atomic spectroscopy database line data, the author analyzed the detailed spectral atomic lines of the dominated elements. With the help of principal component analysis in the Chemometrics, the identification model was constructed under the method of cross-validation. Besides, all kinds of potential influence were analyzed for the detailed model. The result showed us vividly that the laser induced breakdown spectroscopy combined with the principal component analysis had the capacity to discriminate different plastic materials. It gave us a new method for model building and material discrimination. These results can be useful for further research on laser induced breakdown spectroscopy for the differentiation of different materials.