A computational fluid dynamics (CFD) simulation of gas–liquid–liquid three-phase flow was carried out on an annular centrifugal contactor. An Euler–Euler, volume-of-fluid, multiphase-flow model was used for the three-phase flow simulation. The three-phase flow behaviors in the open and sealed inlet operation modes were investigated under various operating conditions. The location and morphology of the aqueous/organic interface were discussed in detail in light of the simulated pressure distribution. An interesting bistability phenomenon was observed in the simulation. The throughput of the annular centrifugal contactor was obtained from the simulation under various phase ratios and compared with experimental results. Excellent agreement was obtained, supporting the validity of the simulation method.