This work presents the enhancement of Cl-/SO42- mono-selectivity of layered nanocomposite anion exchange membranes (AEMs) and the mechanism that supports this improvement. These nanocomposite membranes are based on commercial polyethylene AEMs and a nanocomposite negative thin layer composed of sulfonated poly (2,6-dimethyl-1,4-phenylene oxide) and a functionalized nanomaterial, Fe2O3-SO42- nanoparticles or oxidized multi-walled carbon nanotubes CNTs-COO-. The mechanism for monovalent selectivity was confirmed by characterizing nanocomposite membranes and commercial heterogeneous ion exchange membranes (IEMs) using zeta-potential and electrochemical impedance spectroscopy (EIS). zeta-potential measurements confirmed the modification of the charge of surface of the membrane after being coated with the nanocomposite layer. EIS measurements showed a totally different electrical performance between layered nanocomposite membranes and commercial IEMs. The electrical data from EIS was fitted to a Maxwell-Wagner model providing an equivalent electric circuit (EEC) for each membrane. The observed differences in ECC were related to the structural differences of the membranes. A physical explanation of the phenomena that caused these differences is provided. The influence of ion concentration on EIS measurements was also studied. To the best of our knowledge, this is the first time that an ECC related to the structure of advanced layered IEMs is proposed.