The classification of seven kinds of plastic (ABS, PET, PP, PS, PVC, HDPE and PMMA) with the laser-induced breakdown spectroscopy based on artificial neural network model was investigated in the present paper. One hundred seventy LIBS spectra for each type of plastic were collected. Firstly, all 1 190 plastics LIBS spectra were studied with principal component analysis. The first five principal components (PC) totally explain 78.4% of the original spectrum information. Therefore, the scores of five PCs of 130 LIBS spectra for each kind of plastic were chosen as the training set to build a back-propagation artificial network model. And the other 40 LIBS spectra of each sample were used as the testing set for the trained model. The classification accuracy was 97.5%. Experimental results demonstrate that plastics can be classified by using principal component analysis and artificial neural network (BP) method.