We have demonstrated the effectiveness of the PL technique for quantifying donor and acceptor impurities and for analyzing dislocations and oxygen precipitates in Si. A clear explanation is given of the systematic variation of PL spectra depending on the donor and acceptor concentrations in Si at cryogenic temperatures. On the basis of this spectral variation we developed the PL method for quantitative impurity analysis. The JIS/SEMI standard method was extended to 1×1014 - 1×1017 cm-3 by raising the sample temperature. Further extension to 1×1018 cm-3 was proposed by utilizing the universal peak shift of the ICBE band. DA pair luminescence in highly doped and highly compensated Si allowed us to identify the species of impurities and to extract quantitative information by its intensity comparison with the ICBE band. We identified the origin of the 0. 8 eV band as the superposition of two dislocation-related components at approximately 0.79 and 0.94 eV, and one oxygen-precipitation-related component at about 0.87 eV. The presence of oxygen precipitates was confirmed by mass spectroscopy and by oxygen mapping after luminescence activation. Anisotropic properties expected for the dislocation-related component were revealed by polarized luminescence imaging.