Liquid‐liquid swirling flow is directly affected by the dynamic behavior of discrete droplets. Large eddy simulation combined with the volume‐of‐fluid model (LES‐VOF) was adopted to simulate the dynamic behavior of a CCl4 single droplet under water in a concave‐wall jet. There were three modes of droplets: non‐breakup, binary‐breakup, and multiple‐breakup droplets. The binary‐breakup droplet was sheared by the layer between the jet and the main flow, and the multiple‐breakup droplet was sheared by the boundary layer of the wall. Deformation and breakup were the processes of balancing the internal and external droplet vorticity. The largest pressure difference between the internal and external side of the liquid film was the primary reason for droplet breakup.