In this paper, the coupled transport of vanadium(IV) through supported liquid membranes containing bis(2-ethylhexyl)phosphoric acid was modeled. The experiments were carried out in a stirred permeation cell with a well-defined hydrodynamics. The possibility of the application of the measured transport rates for determining the kinetic parameters of solvent extraction reaction was also investigated. The calculated rates were found to be in good agreement with the measured ones (average standard error, 5%). Under the conditions studied, the transport process was mainly governed by interfacial chemical reaction and partly by combined membrane diffusion in some runs.