Effects of TiO2 on crystalline phase of mold fluxes were studied by the mineral phase microscope and the XRD. The results showed that on the experimental condition, the main crystalline phase of mold fluxes were cuspidine, wollastonite and melilite. When TiO2 added into the mold fluxes, perovskite would be found. TiO2 promoted Perovskite to crystallization and limited Cuspidine to growth. The morphologies and content of wollastonite and melilite were greatly affected by TiO2 adding, especially, as 20% TiO2 added into the mold fluxes.