Gallium (Ga)-containing compounds such as Gallium Arsenide (GaAs) and Gallium Nitride (GaN) are widely used in electronic devices due to their superior electro-optical properties and their usages increase rapidly. For the sustainable supply of Ga to electronic industry, therefore, the recycling of Gallium becomes essential. Pyrometallurgical Ga recycling process involves the complex chemical reactions between slag, matte, liquid metal, gas, refractories, etc. Therefore, the accurate thermodynamic information and phase diagram data for the oxide system containing Ga2O3 is important. In the present study, new phase diagram experiments for binary SiO2-Ga2O3 and ternary CaO-SiO2-Ga2O3 system are carried out using Differential Thermal Analysis (DTA) and quenching experiments followed by Electron Probe Micro-Analyser (EPMA) and X-Ray Diffraction (XRD) phase analysis. Based on new phase diagram data and available literature data, the thermodynamic modelling of the entire CaO-SiO2-Ga2O3 system is performed for the first time.