In this study, we demonstrate that the self-organization of Fe-Ni-Ru alloy@FeOx (FNR@FeOx) coreshell nanoparticles on the Sr2Fe1.5Mo0.4Ni0.05Ru0.05O6-δ (SFMNR) electrode surface in a SOER markedly enhances concurrent electrochemical production of propylene from propane at the anode and CO from CO2 at the cathode. Depth-profiling X-ray photoelectron spectroscopy reveals that these core-shell nanoparticles increase the concentration of active oxygen species at the surface, resulting in a drastic reduction of the activation energy of polarization resistance from 2.1 eV to 0.82 eV. This enhancement yields a high current density of 1.3 A/cm² at 1.6 V and 750 °C, achieving nearly 100% Faradaic efficiency and stable operation for 150 h, alongside 80% selectivity for propylene and ethylene production at 650°C. Density functional theory (DFT) calculations suggest that the observed improvements in the SOER are attributed to the reduced activation energy for dissociative CO2 reduction on the surface of FNR@FeOx core-shell nanoparticles. The self-organization of FNR@FeOx core-shell nanoparticles under reaction conditions was systematically investigated using in situ X-ray diffraction and transmission electron microscopy. These results show the potential of the self-organized core-shell nanoparticles in SOERs for achieving efficient, economically viable CO2 recycling, advancing the goal of a sustainable carbon-neutral society.