A supported liquid membrane (SLM), impregnated with tricaprylmethyl ammonium chloride (Aliquat 336) as a carrier, was investigated for separating and recovering Cr(VI) in aqueous solutions containing Cr(III). It was found that the transport of Cr(VI) through the SLM was dominated by membrane diffusion and that the Aliquat 336 in the SLM played a key role in the selective transport of Cr(VI) while omicron-nitrophenyl octyl ether (NPOE) assisting mobility of the ion-carrier complex in the membrane. The maximum recovery of Cr(VI) in the test solution containing Cr(III) was 93.2% with a permeability of 1.01 X 10(-3) cm/s through the SLM made of 0.0735 g poly(vinyl chloride) (PVC), 0.1471 mL NPOE, and 5.43 x 10(-5) mol Aliquat 336 for a sheet of 24.6 cm(2). The permeability of Cr(VI) was not influenced by concentrations of Cr(VI) and cationic interferences in the feed solution, except for Cr(III). Selective recovery of Cr(VI) in the presence of anionic interferences and Cr(III) was attained reasonably when the nitrate, nitrite, and Cr(III) concentrations did not exceed tenfold of the Cr(VI) concentration.