Ti is an important constituent for steels and superalloys. During the continuous casting process and ElectroSlag Remelting process (ESR), Ti in molten steel and superalloy can have chemical reactions with casting flux and ESR slag containing CaO and CaF2. In order to investigate such exchange reactions, the understanding of the (Ca,Ti//O,F) reciprocal slag system is prerequisite. In the present study, a coupled phase diagram experiment and thermodynamic modelling of the (Ca,Ti//O,F) reciprocal system was performed. In particular, the phase diagram of the CaF2-TiO2 system was experimentally investigated by Differential Thermal Analysis (DTA) experiment and quenching experiments followed by Electron Probe MicroAnalysis (EPMA) phase analysis. The Gibbs energy functions of all solid and liquid phases in the (Ca,Ti//O,F) reciprocal system were optimised to reproduce the present data and all available reliable experimental data in literature.