Transport through a polysaccharide gel phase has been investigated voltammetrically using both redox voltammetry at a gel covered electrode and ion transfer voltammetry across the gel/liquid interface (Gel/L). The apparent diffusion coefficients, D-app, of a range of neutral and ionic electroactive species have been determined in both uncharged and anionic polysaccharide media, agar, and kappa-carrageenan, respectively. It is shown that the diffusion of electroactive species in agar get occurs at a rate similar to that of diffusion in aqueous solution for a range of redox couples. In the kappa-carrageenan medium, by contrast, the diffusion coefficient obtained for cationic solutes was found to be approximately an order of magnitude lower than the value in aqueous Solution. The difference in D-app is attributed to two independent processes: electrostatic interactions between the charge of the sulfonate groups of the kappa-carrageenan gel and the charge of the solute, as well a change in hydration of the solute molecules.