Hexavalent chromium, Cr(VI), is carcinogenic and mutagenic to the living organisms, and hence more hazardous than other heavy metals. The choice of Cr(VI) removal adsorbents has always been a hot issue in environmental protection. Here we report a novel inorganic biocomposite membrane, layered double hydroxide/eggshell membrane (LDH/ESM) as adsorbent for Cr(VI) removal, in which ESM serves as the substrate and template to immobilize the LDH formed by an in situ hydrothermal crystallization method. X-ray diffraction (XRD) and scanning electron microscope (SEM) images showed that MgAl-CO32--LDH grown on the fibers of ESM, and the final LDH/ESM composite membrane both maintained the network structure of the ESM substrate. After being treated with an NaCl/HCl mixed solution, the interlayer CO32- anions in the LDH portion of the composite membrane were exchanged for Cl-. The ESM, MgAl-CO32--LDH/ESM and MgAl-Cl--LDH/ESM composite membrane were evaluated as adsorbent to remove Cr(VI), respectively, and the effect of the pH values on the adsorption was mainly investigated. It showed that the MgAl-Cl--LDH/ESM composite membrane had a higher adsorption capacity than ESM and MgAl-CO32--LDH/ESM even when the pH value of the Cr(VI) solution was not further adjusted by addition of acid, which is of practical significance in a wastewater treatment plant. The adsorption isotherm of the MgAl-Cl--LDH/ESM composite membrane showed a good fit with the Langmuir isotherm model. (C) 2010 Elsevier B.V. All rights reserved.