FTIR spectroscopy has been employed to investigate the structure of CaF2-B2O3 glasses. It is proposed that CaF2 partially modifies the borate network forming Ca-1/2(2+)[BO3/2F](-) units. The rest of CaF2 is assumed to build an amorphous network formed of CaF4 tetrahedra. Analysis of density and molar volume revealed that the volume of CaF4 tetrahedron in the studied glasses is slightly greater than that in the crystalline form. Data of density, molar volume, and electric conductivity have been correlated with the glass structure. As far as the authors know, CaF2-B2O3 glasses are investigated for the first time.