Flow instabilities occurring in rotating flows can be exploited as a new approach to liquid–liquid extraction. Two immiscible liquids are radially stratified by centrifugal force in the annulus between corotating coaxial cylinders. When the inner cylinder is rotated above a critical speed, Taylor vortices form in one or both of the fluids. Although the flow pattern yields a relatively small amount of interfacial surface area, the surface is highly active for interphase mass transfer due to the local vortex motion. By adding countercurrent axial flow, efficient continuous processing is also possible. This flow yields a viable extraction process, particularly for fluid pairs that are easily emulsifiable and therefore have limited processing options with the current equipment commercially available. This article demonstrates that two-fluid Taylor-Couette flow with countercurrent axial flow is achievable in practice and explores, experimentally and computationally, the mass-transfer characteristics of the flow. Experimentally, when the vortices first appear, axial dispersion decreases and the interphase mass transfer starts to increase. Upon further increase in differential rotation rate, the extraction performance continues to improve, with the mass-transfer coefficient proportional to the strength of Taylor vortices. This suggests that very high extraction efficiencies can be obtained with even larger relative rotation rates. Furthermore, mass-transfer boundary-layer theory, in combination with computational fluid dynamics, provides a reliable method for predicting the extraction performance.