We estimated the ion diffusion constant of polymer gel electrolytes in sub-micrometer porous electrode. The ion diffusion constant is an important factor which could determine the cell performance. The porous electrode was fabricated by using sub-micrometer polymer colloid crystals as a template. We evaluated the effective diffusion constant in iodine based PGEs and cobalt based PGEs penetrated into the sub-micrometer porous electrodes and compared to that of the nanoporous conventional electrode which was obtained by cyclic voltammetry. The pore-effective diffusion constant of iodine-based polymer gel electrolyte was 6.81 x 10^-5 for sub-micrometer porous electrode and 4.78 x 10^-6 for the nanoporous electrode. The pore-effective diffusion constant for sub-micrometer porous electrode was enhanced 16% compared to conventional electrode. From this result, the enhancement in pore-effective diffusion was attributed by the sub-micrometer pores. In case of cobalt based electrolytes, the pore-effective diffusion constant was improved 19% by sub-micrometer porous structures as well. In the respect of these results, the pores are demonstrated to assist ion diffusion of polymer gel electrolytes through electrode regardless of redox complex. In particular, the pores are more effective to increase pore-effective diffusion constant under the bulky redox complex electrolytes condition.