Perovskite　oxides　have　emerged　as　alternative　anode　materials　for　hydrocarbon-fueled　solid　oxide　fuel　cells　(SOFCs).　Nevertheless,　the　sluggish　kinetics　for　hydrocarbon　conversion　hinder　their　commercial　applications.　Herein,　a　novel　dual-exsolved　self-assembled　anode　for　CH4-fueled　SOFCs　is　developed.　The　designed　Ru@Ru-Sr2Fe1.5Mo0.5O6-δ(SFM)/Ru-Gd0.1Ce0.9O2-δ(GDC)　anode　exhibits　a　unique　hierarchical　structure　of　nano-heterointerfaces　exsolved　on　submicron　skeletons.　As　a　result,　the　Ru@Ru-SFM/Ru-GDC　anode-based　single　cell　achieves　high　peak　power　densities　of　1.03　and　0.63 W cm−2　at　800 °C　under　humidified　H2　and　CH4,　surpassing　most　reported　perovskite-based　anodes.　Moreover,　this　anode　demonstrates　negligible　degradation　over　200 h　in　humidified　CH4,　indicating　high　resistance　to　carbon　deposition.　Density　functional　theory　calculations　reveal　that　the　created　metal-oxide　heterointerfaces　of　Ru@Ru-SFM　and　Ru@Ru-GDC　have　higher　intrinsic　activities　for　CH4　conversion　compared　to　pristine　SFM.　These　findings　highlight　a　viable　design　of　the　dual-exsolved　self-assembled　anode　for　efficient　and　robust　hydrocarbon-fueled　SOFCs.　©　2023　The　Authors.　Advanced　Science　published　by　Wiley-VCH　GmbH.