In this study the transport of chromium(VI) from aqueous solutions of pH 2-4 through a supported liquid membrane (SLM) with tri-n-octylphosphine oxide (TOPO) dissolved in kerosene as a mobile carrier was investigated. The transport flux of Cr(VI) increased with an increase in the concentrations of Cr(VI) in the feed phase and of TOPO in the membrane phase, but with a decrease in pH of the feed phase. Considering the equilibria of various Cr(VI) species in the aqueous phase and of the Cr(VI)-TOPO complexes formed in the membrane phase, a permeation model including the aqueous film diffusion of HCrO4- and Cr2O72-toward the membrane, the interfacial chemical reaction between them and TOPO, and the membrane diffusion of the Cr(VI)-TOPO complexes (H2CrO4(TOPO) and H2Cr2O7(TOPO)(3)) was proposed to describe the transport of Cr(VI) through the SLM. By best fitting the transport flux equations of Cr(VI) with the experimental data using the Rosenbrock method, the apparent mass-transfer coefficients of HCrO4- and Cr2O72- across the aqueous film, and those of H2CrO4(TOPO) and H2Cr2O7(TOPO)(3) across the membrane phase, were obtained. This work helps to clarify the transport mechanism of Cr(VI) through an SLM.