Bubble collapse near the liquid–liquid interface was experimentally studied in this paper, and the dynamic evolution of a laser-induced bubble (generation, expansion, and collapse) and the liquid–liquid interface (dent and rebound) were captured by a high-speed shadowgraph system. The effect of the dimensionless distance between the bubble and the interface on the direction of the liquid jet, the direction of bubble migration, and the dynamics of bubble collapse were discussed. The results show that: (1) The jet generated during bubble collapse always directs toward the denser fluid; (2) bubble collapses penetrate the interface when the bubble is close to the interface; (3) three different shapes of the liquid–liquid interface—that is, a mushroom-shaped liquid column, a spike droplet, and a spherical liquid droplet—were observed.