Raman spectra have been measured for pellets of five samples of high-density polyethylene (HDPE), seven samples of low-density polyethylene (LDPE), and six samples of linear low-density polyethylene (LLDPE). The obtained Raman spectra have been compared to find out characteristic Raman bands of HDPE, LDPE, and LLDPE. Principal component analysis (PCA) was applied to the Raman spectra in the 1600-650 cm(-1) region after multiplicative scatter correction (MSC) to discriminate the Raman spectra of the three different PE species. They are classified into three groups by a score plot of PCA factor 1 vs. 2. HDPE with high density and high crystallinity gives high scores on the factor I axis, while LDPE with low density and low crystallinity yields negative scores on the same axis. It seems that factor I reflects the density or crystallinity. A PC weight loadings plot for factor I shows six upward peaks corresponding to the bands arising from the crystalline parts or all-trans -(CH2)(n)- groups and seven downward peaks ascribed to the bands of the amorphous or anisotropic regions and those arising from the short branches. Partial least-squares (PLS-1) regression was applied to the Raman spectra after MSC to propose calibration models that predict the density, crystallinity, and melting points of the polyethylenes. The correlation coefficient was calculated to be 0.9941, 0.9800, and 0.9709 for the density, crystallinity, and melting point, respectively, and their root-mean-square error of cross validation (RMSECV) was found to be 0.0015, 3.3707, and 2.3745, respectively. The loadings plot of factor 2 for the prediction of melting point is largely different from those for the prediction of density and crystallinity.