External-beam PIXE was used for the non-destructive analysis of early glasses unearthed from the tombs of Warring States (475–221BC) and Han Dynasty (BC 206–AD 220) in south China. It was found that these glasses were basically attributed to PbO—BaO—SiO2 system and K2O—SiO2 system. The results from the cluster analysis showed that some glasses had exactly the same recipe. The source of the K2O flux and the correlation between PbO and BaO are discussed. Some archeological information is revealed.