Ionomers such as Nafion are being used for engineering the microenvironment of the CO2RR towards selectivity to higher hydrocarbons. Their cationic exchange qualities mitigate homogeneous bicarbonate reactions, providing favourable conditions for production of C2-C3 products. The proximity of Nafion® layers to the negatively charged electrode surface results in complex effects that have yet to be explored computationally. We combine mass transport equations and density functional theory (DFT) calculations to model the hydrophilic moieties in Nafion® layer on a 1D planar copper electrode. We vary the Nafion® layer thickness in the thick film regime (200–1100 nm), the ionic strength of supporting aqueous electrolyte and the applied voltage to investigate the concentration profile of participating species within the Nafion® layer. We find that the bicarbonate ion concentration and local pH decrease with decreasing thickness which makes thinner films better at mitigating bicarbonates at the cost of a relatively lower pH. We observe the breakdown of Donnan exclusion effects with higher ionic strength electrolytes which allows diffusion of both co-ions and counter-ions, promoting the bicarbonate reactions. Further, we find that the pKa of Nafion® generally increases as the local dielectric constant of the reaction medium decreases. This is primarily due to the accumulation of K+ and production of low dielectric constant products such as ethanol, albeit their concentrations are low on planar Cu electrodes. The lower permittivity of the reaction medium weakens the exclusion forces and changes the morphology of Nafion® which ultimately impacts its ability to mitigate homogeneous bicarbonate reactions.