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Porous electrodes with increased surface area have been prepared using a template route via colloidal crystals. The ordered porous structure and the interconnections between the pores have been quantitatively characterized by Focused Ion Beam Tomography. The internal surfaces of the electrodes have been biofunctionalized with two enzymatic systems for glucose oxidation. In order to increase significantly the stability, the biocatalysts have been immobilized either by crosslinking or by incorporation in an electrodeposition paint. The modified porous electrodes show an increased overall signal and therefore a better detection limit and a higher sensitivity when used as sensors, and a potentially higher power output when employed in biofuel cells.