Raman spectra of antimonate mineral brizziite NaSbO3 were studied and related to the structure of the mineral. Two sharp bands at 617 and 660 cm-1 are attributed to the SbO ? symmetric stretching mode. The reason for two symmetric stretching vibrations depends upon the bonding of the SbO ? units. The band at 617 cm-1 is assigned to bonding through the Sb and 660 cm-1 to bonding through the oxygen. The low intensity band at 508 cm-1is ascribed to the SbO antisymmetric stretching vibration. Low intensity bands were found at 503, 526 and 578 cm-1. Sharp Raman bands observed at 204, 230, 307 and 315 cm-1 are assigned to OSbO bending modes. Raman spectroscopy enables a better understanding of the molecular structure of the mineral brizziite.