Metallurgical slag, such as refining slag, is essential to enhance or promote steel cleanliness. The CaO–MgO–Al2O3–SiO2 system is the primary source of oxides-based inclusions. It plays a vital role in applications in various pyrometallurgical processes. Numerous thermodynamic databases and physicochemical properties of slag studies mainly focus on quenched samples and measurements at room temperature. Consequently, the present study explored the physicochemical, structural properties and crystallisation evolution for CaO–MgO–Al2O3–SiO2 glassy slags via in situ hightemperature Raman spectroscopy and synchrotron X-ray diffraction. The study was carried out by synthesising CaO–MgO–Al2O3–SiO2 slag with varying Al2O3/SiO2 ratios. The results from the in situ high-temperature measurement demonstrated a pattern showing a transformation of a broad peak from the glassy matrix to crystalline peaks. The study showed crystallisation of dominant phases such as Ca2SiO4, Ca2Al2SiO7 and CaAl2O4 that correspond and are attributable to changes of structural units during in situ high-temperature measurements. The results further showed a correlation between an increase and transformation in crystalline phases observed from the spectra obtained from non-isothermal heating of the samples.