In the last decades, several works have been carried out on solid oxide fuel cell (SOFC) and solid oxide electrolysis cell (SOEC) technologies, as they are powerful and efficient devices for energy conversion and electrochemical storage. By increasing use of renewable sources, a discontinuous amount of electricity is indeed released, and reliable storage systems represent the key feature in such a future energy scenario. In this context, systems based on reversible solid oxide cells (rSOCs) are gaining increasing attention. An rSOC is an electrochemical device that can operate sequentially between discharging (SOFC mode) and charging (SOEC mode); then, it is essential the electrodes are able to guarantee high catalytic activity, both in oxidation and reduction conditions. Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) has been widely recognized as one of the most promising electrode catalysts for the oxygen reduction reaction (ORR) in SOFC technology because of its astonishing content of oxygen vacancies, even at room temperature. The purpose of this study is the development of BSCF to be used as anode material in electrolysis mode, maintaining enhanced energy and power density. Impregnation with a La0.8Sr0.2MnO3 (LSM) discrete nanolayer is applied to pursue structural stability, resulting in a long lifetime reliability. Impedance spectroscopy measurements under anodic overpotential conditions are run to test BSCF and LSM-BSCF activity as the electrode in oxidation mode. The observed results suggest that BSCF is a very promising candidate as an oxygen electrode in rSOC systems.