A durable high-performance anode with a unique microstructure of a hetero-structured surface layer and exsolved Fe-Cu bimetal nano-fibers is fabricated from a self-assembled dual-phase precursor consisting of a single perovskite (SP) and a Ruddlesden-Popper (RP) layered perovskite component. This work opens up new opportunities to fabricate high-performance anodes for IT-SOFCs.