For applying the Laser Induced Breakdown Spectroscopy technology to the ancient pottery(Lingjiatansite, 3000BC, Anhui, China) research, the goal and aim is for quick identificationand classification of the different types of ancient ceramic wares. Lingjiatan Site, located in Hanshan County, Maanshan City, Anhui Province, China, is a large late Neolithic settlement in southern China. A large number of fine jade articles, stone ware and pottery have been unearthed from the site. It is an important site!for studying the origin of earlyChinese civilization. Therefore, the study of its pottery is of great cultural and historical significance. After LIBS analysis, using the principal component analysis to process the data and give the reference to the classification workof pottery. The results show that different temper in body of pottery will affect the characters of spectrum and the PCA could give the classification group based on those spectra discrepancies. In the other hand, due to the consideration of statistical analysis, the abnormal data interference such as background noise is purposefully reduced and classified, and the characteristic spectral lines are extracted based on the attribution of the element spectral lines, thus realizing the purpose of rapid classification by multivariate statistical analysis. The results show that compared with pure argillaceous pottery, the samples of temper of plant pottery and some fine sand temper have well discrimination in LIBS spectral characteristics and can be effectively distinguished. According to the actual situation, other types of processing and materials need to be judged comprehensively with other means. This work indicates that the LIBS and PCA will be suitable and useful tools for ancient ceramics research.