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Ion-exchange membranes (IEMs) represent a key component in various electrochemical energy conversion and storage systems. In this study, electrochemical impedance spectroscopy (EIS) was used to investigate the effects of structural changes of anion exchange membranes (AEMs) on the bulk membrane and interface properties as a function of solution pH. The variations in the physico/electrochemical properties, including ion exchange capacity, swelling degree, fixed charge density, zeta potentials as well as membrane and interface resistances of two commercial AEMs and cation exchange membranes (CEMs, as a control) were systematically investigated in different pH environments. Structural changes of the membrane surface were analyzed by Fourier transform infrared and X-ray photoelectron spectroscopy. Most notably, at high pH (pH > 10), the membrane (R_m) and the diffusion boundary layer resistances (R_dbl) increased for the two AEMs, whereas the electrical double layer resistance decreased simultaneously. This increase in R_m and R_dbl was mainly attributed to the deprotonation of the tertiary amino groups (-NR₂H⁺) as a membrane functionality. Our results show that the local pH at the membrane-solution interface plays a crucial role on membrane electrochemical properties in IEM transport processes, particularly for AEMs.