The capillary interactions are prominent for a micro-sized particle at the steel–slag interface. In this study, the dynamics of a spherical particle interacting with the steel–slag interface is numerically investigated using the volume of fluid method in combination with the overset grid technique to account for particle motion. The simulations have shown the particle’s separation process at the interface and successfully captured the formation and continuous evolution of a meniscus in the course of particle motion. A sensitivity analysis on the effect of different physical parameters in the steel–slag–particle system is also conducted. The result indicates that the wettability of particle with the slag phase is the main factor affecting particle separation behavior (trapped at the interface or fully separated into slag). Higher interfacial tension of fluid interface and smaller particle size can speed up the particle motion but have less effect on the equilibrium position for particle staying at the interface. In comparison, particle density shows a minor influence when the motion is dominated by the capillary effect. By taking account of the effect of meniscus and capillary forces on a particle, this study provides a more accurate simulation of particle motion in the vicinity of the steel–slag interface and enables further investigation of more complex situations.