The centrifugal force field in a hydrocyclone was affected by the concave-wall curvature radius R0, and the mechanism underlying droplet deformation was closely related to the mass transfer efficiency. Numerical simulation and experimental data were collected to reveal the deformation characteristics and mechanism of a single droplet crossing concave-wall jet. Normalized interfacial energy γ and stretching performance were provided to investigate the droplet deformation process. The results showed that the droplet was stretched along the streamwise direction and shrank along the spanwise direction in the concave-wall jet. The droplet interfacial energy and deformation were the largest when the droplet crossed the jet boundary at t = 0.20 s. The maximum γ value increased with the increase in R0 by 57.3% to 71.4%, and the distance between the droplet and concave wall increased with R0. The Q-criterion was exported to show the increase in the vortex strength with the decrease in R0 at the jet boundary. The pressure distribution inside the droplet showed that the pressure decreased as R0 increased, while the pressure difference increased along the streamwise and wall-normal directions. This study suggested that the droplet breakup was more difficult for a smaller R0, which was beneficial for liquid–liquid heterogeneous separation.