Development of fluoride-free mould flux is important for steel continuous casting. Properties of the mould flux depend on the flux crystallinity. This paper analyzes phase composition of fluxes containing B 2 O 3 , TiO 2 , Na 2 O, and MgO which can be feasible candidates to replace the fluorides. The phase equilibria of these fluoride-free boracic mould fluxes were calculated using the thermochemical software FACTSage. In the process of crystallization of the CaO-SiO 2 -Al 2 O 3 -B 2 O 3 -Na 2 O flux with high CaO/SiO 2 , combeite (Na 2 , Ca)Na 2 CaSi 3 O 9 , Ca 11 B 2 Si 4 O 22 , and nepheline NaAlSiO 4 were formed, which can substitute cuspidine in the fluoride-containing fluxes. At high CaO/SiO 2 , adding MgO into CaO-SiO 2 -Al 2 O 3 -B 2 O 3 -Na 2 O-TiO 2 mould flux remarkably increased crystallization temperature by forming merwinite (Ca 3 MgSi 2 O 8 ), decreasing the relative crystal phase contents of (Na 2 ,Ca) Na 2 CaSi 3 O 9 and Ca 11 B 2 Si4O 22 . The calculated data were in reasonable agreement with results of XRD and SEM/EDS analyses of selected boracic fluxes.