Ion-exchange membranes hybridized with laser-induced graphene (LIG) might lead to membranes with functional surface effects such as antifouling, antibacterial, or joule heating effects; however, understanding the change in the electrical properties of the membrane is essential. Here we studied LIG-modified ion-exchange polymeric membranes using electrochemical impedance spectroscopy (EIS). The conductivity of the anionic sulfonated poly­(ether sulfone) membranes and the effective capacitance of the membrane–electrolyte interface were obtained by fitting the EIS spectra to an electrochemical equivalent circuit and compared with LIG-modified nonionic poly­(ether sulfone) films. The transport selectivity (as the relative permeability) of counterions (K+, Na+, Mg2+, Ca2+) across the membrane was quantified using the membrane’s conductivities obtained from the EIS measurements. The total ohmic resistance of the membrane was directly correlated to the polymer thickness (with negligible contribution from the conductive LIG layer), thereby establishing EIS as a rapid, low-cost, and noninvasive method to accurately probe substrate usage in LIG modification.