Cu-based cermets suitable for electrodes in Symmetric and Reversible Solid Oxide Fuel Cells (SR-SOFCs) based on the Cerium Gadolinum Oxide (CGO) electrolyte were developed and successfully tested in the intermediate temperature range (600-800 °C). The Cu/CGO cermets were prepared by means of a self-combustion based citrate procedure and the effects of synthesis conditions were studied. Characterization of the Cu/CGO nanocomposites by XPS, XRD, SEM, TPR suggested that this procedure allows obtaining highly dispersed CuO on the cerium gadolinium oxide. Conversion higher than 80% was observed above 600 °C in methane total oxidation. Synthesis parameters affected both properties and catalytic performance. The behaviour under redox conditions was studied by operando high-energy XRD under oscillating H₂/O₂ feed. Reducing conditions converted CuO into Cu(0) passing through an intermediate Cu₂O phase while increasing the conductivity and the reactivity. This structural modification was completely reversible. The high stability, reversibility, catalytic activity and electrochemical performance make these electrodes promising for SR-SOFCs.