The objective of the present work is to get an understanding of the impact of Al2O3 addition on the phase relationships in the CaO–MgO–Al2O3–SiO2–Cr2O3 slags at low oxygen partial pressures ( = 10−4 Pa), with a view to control the precipitation of Cr-spinel in the slag. The equilibrium phases in CaO–MgO–Al2O3–SiO2–Cr2O3 slag system in the range on 1673–1873 K have been investigated. The compositions close to the industrial slag systems were chosen. The Cr2O3 content was fixed at 6 wt% and MgO at 8 wt%. Al2O3 contents in the slag were varied in the range of 3–12 wt%. The basicity (CaO/SiO2) of slag was set to 1.6. Gas/slag equilibrium technique was adopted. The samples were heated to 1873 K and soaked at this temperature for 24 h. The samples were then slow cooled to 1673 K and equilibrated for an additional 24 h. The oxygen partial pressure was kept at 10−4 Pa. A gas mixture of CO/CO2 was used to control the oxygen partial pressure. After the equilibration, the samples were quenched in water. The chromium distribution and phase compositions in the quenched slags were studied using SEM–WDS and XRD techniques. The results were compared with the phase equilibrium calculations obtained from FACTSAGE software and the samples equilibrated in air. The size of spinel crystals increased drastically after slow cooling followed by annealing compared to samples being quenched after soaking at 1873 K. It was also found that low oxygen partial pressure had a strong impact on chromium partition. The amount of spinel phase increases with increased Al2O3 content.