This study demonstrates the potential of Fe-Ni-Ru alloy@FeOx core-shell nanoparticles on the Sr2Fe1.5Mo0.4Ni0.05Ru0.05O6-δ (SFMNR) electrode surface to enhance solid oxide electrochemical reactor technologies for the concurrent, separated production of CO and propylene. Annealed under reducing conditions, these nanoparticles exhibit a distinct structural and compositional profile that enhances catalytic and electrochemical performance. Depth-profiling XPS and TEM analyses confirm a core-shell structure stabilized on the perovskite oxide surface via cation valence modulation, which increases the surface concentration of active oxygen species. Electrochemical evaluations demonstrate that the FNR@FeOx coreshell nanoparticles substantially reduce polarization resistance and activation energy in a CO2 environment.