As part of the ternary system Na3AlF6-Na2B4O7-TiO2, the binary subsystem: Na2B4O7-TiO2 and the pseudobinary subsystem Na2B4O7-[Na3AlF6-TiO2]e were investigated. The phase diagrams established by DTA measurements evidenced a simple eutectic point for both systems except for the concentration range > 85 wt. % Na2B4O7 of the Na2B4O7-[Na2AlF6-TiO2]e system where the binary paragenesis rules are no longer obeyed. Additional information regarding the structure of the mixtures were obtained by X-ray diffraction and Raman spectroscopy. Both vitreous and crystalline state were evidenced, without any new compound formation. The presence of titanium, mainly as TiO4 tetrahedra, was also proved.