The modification of MgO·Al₂O₃ spinel inclusions in Al-killed steel by Ca-treatment has been studied by industrial trials and thermodynamic calculations. In the industrial trials, samples were taken systematically during the refining process in which the molten steel was treated by calcium, and the characters of the inclusions were analyzed using scanning electron microscopy (SEM) and energy dispersive spectra (EDS). The effects of Ca-treatment were evaluated by tracking the compositions of the inclusions. The results show that the modification of MgO·Al₂O₃ spinel inclusions by Ca-treatment is effective and the transformation sequence of the inclusions during the refining is Al₂O₃→MgO·Al₂O₃→liquid complex inclusions. The modification of spinel inclusions by Ca-treatment was calculated by FactSage6.0 utilizing its free-energy minimization routines. The results of thermodynamic calculations indicate that spinel inclusions are easier to be modified than Al₂O₃ inclusions and the spinel inclusions in 30CrMo steel would transform to liquid complex inclusions when the content of dissolved Ca in the molten steel exceeds 1×10^-6. Also, the results show that adding more calcium into the molten steel would lower the contents of Al₂O₃ and MgO and increase the CaO content of the inclusions, while the change in SiO₂ content is little.