The infrared (400-1200 cm(-1)) and Raman (200-1150 cm( 1)) spectra are reported for the new AO(3)-BaF2-RF glasses where A is molybdenum or tungsten and RF is the alkali fluoride LiF, NaF and mixed LiF-NaF respectively. The observed absorption bands of each glass series were assigned to their vibrational modes. This study has shown that structural units formed in these glasses include [MoO4] and [WO4] tetrahedra, [MoO6], [WO6], [MoF6] and [WF6] octahedra groups.