In this paper, a new anodic material, calcium doped cobalt layered perovskite, member of Co-114 mixed oxide family, with electrocatalytic activity for ethanol oxidation reaction (EOR) in aqueous alkaline media (1 M KOH) has been tested, in order to find the relationship between ethanol concentration added in electrolyte and oxidation potential, current density, and oxidation efficiency. Experimental studies are a serious issue, especially due to the possibility of using electrodes based 114 layered cobalt perovskite in direct ethanol fuel cells with alkaline electrolyte. First compound from Co-114 layered perovskite, YBaCo4O7, also named Y-114, has been synthesized since 2002 by Valldor et al [1]. As well, Y0.5Ca0.5BaCo4O7 has been prepared by M. Valldor by half substitution of Y3+ with low valence Ca2+ cations in original Y-114 structure [2]. Previous studies performed on layered cobalt perovskites type 114 have demonstrated that these compounds can be used as membranes with high oxygen permeability, oxygen sensors and electrodes materials for intermediate temperature solid oxide fuel cells (IT-SOFC) [1-3]. It has been found that, due to the variable cobalt ions valence (+2 and +3) oxygen adsorption properties can be modified greatly by Y3+ ions substitution with small cations, Ca2+ [2]. In order to elucidate the mechanism of EOR which occurs at this perovskite electrodes interface, kinetic parameters were determined using Tafel method. Furthermore, electrochemical impedance spectroscopy studies were performed. Also, for a complete characterisation of ethanol electrooxidation process on this electrode, chronoamperometry, chronopotentiometry, chronocoulometry measurements were conducted. Obtained results have shown that Y0.5Ca0.5BaCo4O7 perovskite electrodes are suitable as anodes in fuel cells.