The hydrodynamic and thermal interaction of water with the high-temperature melt of a heavy metal was studied via the Volume-of-Fluid (VOF) method formulated for three immiscible phases (liquid melt, water, and water vapor), with account for phase changes. The VOF method relies on a first-principle description of phase interactions, including drag, heat transfer, and water evaporation, in contrast to multifluid models relying on empirical correlations. The verification of the VOF model implemented in OpenFOAM software was performed by solving one- and two-dimensional reference problems. Water jet penetration into a melt pool was first calculated in two-dimensional problem formulation, and the results were compared with analytical models and empirical correlations available, with emphasis on the effects of jet velocity and diameter. Three-dimensional simulations were performed in geometry, corresponding to known experiments performed in a narrow planar vessel with a semi-circular bottom. The VOF results obtained for water jet impact on molten heavy metal (lead–bismuth eutectic alloy at the temperature 820 K) are here presented for a water temperature of 298 K, jet diameter 6 mm, and jet velocity 6.2 m/s. Development of a cavity filled with a three-phase melt–water–vapor mixture is revealed, including its propagation down to the vessel bottom, with lateral displacement of melt, and subsequent detachment from the bottom due to gravitational settling of melt. The best agreement of predicted cavity depth, velocity, and aspect ratio with experiments (within 10%) was achieved at the stage of downward cavity propagation; at the later stages, the differences increased to about 30%. Adequacy of the numerical mesh containing about 5.6 million cells was demonstrated by comparing the penetration dynamics obtained on a sequence of meshes with the cell size ranging from 180 to 350 µm.