In open atmosphere the two phases containing fluorine, C11A7∙CaF2 and 3CA∙CaF2, laying in the CaO-CaO∙Al2O3-CaF2 were synthesized. The synthesis of the 3CA∙CaF2 at 1.100°C was possible without loss of F, when the stoichiometric mixture of CA and CaF2 was pressed into tablets and was applied vacuum, avoiding in such a way the presence of moisture. According to TGA studies, the vapour pressure of phases containing fluorine, at 1.100°C is very low and follows this sequence: CaF2 < 3CACaF2 < C11A7∙CaF2. At 1.000°C the system behaves as condensated. Verification of some compatibilities in solid state in the system CaO-CaO∙Al2O3-CaF2 at 1000°C has been done. Compatibility triangles found are the same described by Chaterjee, and different from the compatibilities given by Brisi and Rolando.