Reactive extraction separation of binary amino acids from water using a microporous hollow fiber has been studied, in which the acidic extractant di(2-ethylhexyl)phosphoric acid (D2EHPA) was selected as an active carrier dissolved in kerosene. L-Phenylalanine (Phe) was extracted from an aqueous solution through the shell side of module to the organic phase through the lumen of fiber in the extraction module, in which L-Phe was then back-extracted to stripping phase in stripping module. Experiments were conducted as a function of the initial feed concentration of equimolar Phe and L-aspartic acid (L-Asp) (5 Mol/m(3)), feed pH (3-5), the carrier concentration (0.1-0.5 mol/dm(3)), and stripping acidity (0.1-2 mol/dm(3)). The effect of process variables on the separation factor of Phe/Asp and the possible transport resistances including aqueous-layer diffusion, membrane diffusion, organic-layer, and interfacial chemical reaction were quantitatively studied and discussed. The high separation factor (beta) of Phe/Asp was obtained to be 18.5 at feed pH 5 and 2 mol/dm(3) of strip solution (HCl). The extraction and stripping processes appear to rely on pH dependence of the distribution coefficient of amino acids in reactive extraction system. The separation factor (beta) was enhanced in hollow fiber membrane (HFM) process compared with conventional solvent process, which was a result of the counter transport of hydrogen ions. (c) 2006 Elsevier B.V. All rights reserved.