Raman spectrum of molten cryolite was recorded. Based on the new understanding of the scattering coefficients, contents of various structural entities in acidic NaF-AlF3 melts at 942-1 024 ℃ in previous research were reanalyzed. The new quantitative analysis results show that when cryolite ratio（CR） is less than 2, AlF4- is the dominant anion in the melts, and its mole fraction is about 0.70 for melts with CR=1.5 and 0.50 for melts with CR=2. When CR is more than 2.5, the mole fraction of AlF6^3- is relatively large, which is around 0.45 for melts with CR=2.5. Ionic structure of Na3AlF6-Al2O3 melts was investigated by UV-Raman spectroscopy. Octahedral AlF6^3- and tetrahedral AlF4- are proved to exist with possible partial replacement of F- by O^2-. Al2O2F4^2- with a large scattering coefficient also exists in the melts in which alumina concentration is more than 4% （mass fraction）. The increase of temperature causes blue-shift of the bands in the Raman spectra.
