Electrochemical characteristics for several redox systems at diamond films with highly ordered nanometer-scale cylindrical pores (‘nano-honeycombs’) were examined with cyclic voltammetry (CV) and electrochemical impedance measurements. The cyclic voltammetric anodic–cathodic peak separations for these nano-honeycomb electrodes were in the same range as those for polished polycrystalline diamond films, indicating that the involvement of the oxygen-terminated surface of the nano-pore walls, which should give rise to large peak separations for certain redox couples was only slight. Moreover, the peak currents in the CV were not enhanced to the extent expected on the basis of the roughness factors of the nano-honeycomb films. Ac impedance plots results indicated the existence of a concentration gradient of the reactant in the nano-pores, which is in agreement with theoretical predictions for charge transfer reactions in porous electrodes. The average concentration of the reactant (Fe2+/3+) inside the nano-pores was a factor of ca. 80 lower than that in the bulk electrolyte. The results of the impedance analysis also indicated an increase in the reaction resistances with decreasing pore diameters.