The objective of the present work is to get an understanding of the phase relationships in the CaO-MgO-SiO2-Cr2O3 system with a view to control the precipitation of Cr-spinel in the slag phase. The equilibrium phases in CaO-MgO-SiO2-Cr2O3 slag system at 1873 K (1600°C) have been investigated experimentally and compared with the results from thermodynamic calculations. The Cr2O 3 and MgO contents in the slag were fixed at 6 and 8 wt-% respectively. The basicity (CaO/SiO2) of slag was varied in the range 1·0-2·0. A gas/slag equilibrium technique was adopted to synthesise the slag at a high temperature in air. The samples were heated to and soaked at 1873 K (1600°C) for 24 h in order to achieve the equilibrium state and subsequently quenched in water. The chromium distribution and phase compositions in the quenched slag were studied using scanning electron microscope wavelength dispersive spectroscopy and X-ray diffraction techniques. FactSage software was used for the phase equilibrium calculations. The experimental results obtained from the present work were compared with the calculation results from FactSage software. It was found that the spinel formation at 1873 K (1600°C) is favoured in the slag basicity range 1·0-1·4