Development and application of fluorine free mould fluxes have been widely studied in recent years. Some research has shown that B
2O
3 and TiO
2 are potential substitutes for F
– in mold fluxes. In this study, Structure of CaO–B
2O
3–SiO
2–TiO
2 glass system has been studied by Raman spectroscopy. The influence of basicities (CaO/SiO
2) and contents of B
2O
3 and TiO
2 on the structure of CaO–B
2O
3–SiO
2–TiO
2 glasses were examined. Experimental results indicate that TiO
2 exists in the system in the form of [TiO
4] as network former in range of 0–15% in mass. The degree of polymerization of this system decreases with increase of basicities. The increase of B
2O
3 leads to more [BO
4] tetrahedral units. It is concluded that both B
2O
3 and TiO
2 behave as network forming oxides within the studied system.
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