A highly selective LiMn2O4-Polypyrrole electrochemical cell for the extraction of LiCl from natural brine is described. Reproducible intercalation of Li+ in LixMn2O4 (0 <= x <= 1) and Cl- in oxidized polypyrrole (PPy+) is achieved with an overall cell voltage of less 1 V over more than 200 cycles with 50% charge efficiency and 5-10 Wh.mol(-1) energy consumption. No insertion of Na+ has been observed. (C) 2016 The Electrochemical Society. All rights reserved.