The traditional ways of waste plastics processing mainly use the burning landfill, which lead to environmental pollution and the waste of resources. Waste plastic recycling is very important on the circulation economy and the sustainable development.The traditional instruments have some shortcomings in plastic classification, such as lower precision, higher cost, the influence of the sample color and a serious threat to operating personnel’s health. Laser induced breakdown spectroscopy has many advantages, such as simultaneous multielement detection of elements, free from sample preparation, rapid and real-time analysis, slight damages to sample and no impact on the sample color. The method of Chemometrics combined with LIBS technique is applied to the plastic, which improves the accuracy of plastic classification. But at present,the classification has many problems, such as more parameters and the poor universality. Using on a self built LIBS instrument, we can study the laser energy, delay time, integration time and the angle of the optical fiber, which can achieve a better experiment condition. With the experimental platform, we analyze the 2 200 sample points and choose the partial least squares to analyze the spectral data. In order to achieve the correlation between the sample label and the data, we discuss the better ratio of the training set and validation set. The experimental results show that replacing the interference spectra, classification accuracy of all 11 plastic is increased to 100%, while the validation set’s accuracy is only 99.8% and the test set is 99.09% without replacing the interference spectra . It can be seen that the laser induced breakdown spectroscopy combined with partial least squares method can be successfully used for the plastic sample classification.