In this work, Ca1-xHoxMnO3 (x = 0, 0.1 and 0.2) perovskite oxide pelleted electrodes were prepared from the respective powders obtained by the citrate route method at 1173 K. The electrodes exhibit particle size that decreases with the holmium content in the oxide. All the samples reveal semiconductor behaviour and the presence of holmium induces a marked decrease in the electrical resistivity. The results can be well attributed to the changes in the Mn4+/Mn3+ ratio. Electrodes were characterized by cyclic voltammetry and chronopotentiometry. Cyclic voltammetric studies indicate a similar behaviour of the electrodes, irrespective of their composition. Two pairs of peaks were identified and associated, one to the Mn4+/Mn3+ redox couple and the other to the Mn7+/Mn4+ and Mn6+/Mn4+ redox couples. The voltammetric data provide evidence that the electrodes roughness factor increases with the introduction of Ho-ions in the oxide structure, what is consistent with the crystallite size obtained by X-ray diffraction (XRD) and the morphology observed by scanning electron microscopy (SEM). The Ho-substituted electrodes present higher current density when compared with CaMnO3 electrodes what can be attributed both to higher electrical conductivity and smaller particle size. The chronopotentiometric studies have shown that the discharge Occurs by different mechanisms for the oxide electrodes with and without Ho. (C) 2009 Elsevier Ltd. All rights reserved.