HMs can not only affect the surface chemistry of the electrodes, but they can also affect the permeability of penetrants (e.g. redox species and analytes) . Based on the size and chemistry of penetrants, which affect diffusivity and partitioning throughout the hydrogel, and the physicochemical properties of the hydrogel (e.g. porous structure, surface charge, hydration level and crosslinking density) the permeation of penetrants may change, affecting the electrochemical behavior of the electrochemical system. In other words, in the presence of an HM on the electrode surface, two phenomena may contribute: 1) charge transfer kinetics, because of altered surface chemistry and, 2) permeability change, because of selective permeation throughout HMs. The system is more complex in the vicinity of electrodes, not only because of the concentration gradient and polymer chain-penetrant interactions, but also the external electric field are contributing mechanisms affecting the permeability of penetrants. However, electrochemical methodologies enable the prediction of an effective diffusion coefficient, without measuring the concentration gradient. This work challenges the current state of the art, related to the description of charge transfer through interphase, composed of a highly porous LIG with limited electric conductivity and polysaccharide HMs, introducing varying mass transport effects for an electrochemically active, redox species. We provide an in-depth discussion of Ohmic drop consideration, across porous LIG, as well as the polysaccharide HMs' capability to alter LIG charge transfer, considering cationic (CS), neutral agarose (Agar) and anionic sodium alginate (Alg). Moreover, we reveal how and why LIG operating conditions affect redox process kinetics, emphasizing the importance of lasing optimization, partially limited by the HMs presence. Adequate consideration of electrode-dependent ohmic drop, frequency dispersion of capacitance, as well as the effect of electrostatic interactions, within the HM, on diffusion and the electrochemically active surface area (EASA) introduces new and important LIG characterization features.