A metallic nanoparticle-decorated ceramic anode was prepared by in situ reduction of the perovskite Sr₂FeMo_0.65Ni_0.35O_6−δ (SFMNi) in H₂ at 850 °C. The reduction converts the pure perovksite phase into mixed phases containing the Ruddlesden–Popper structure Sr₃FeMoO_7−δ, perovskite Sr(FeMo)O_3−δ, and the FeNi₃ bimetallic alloy nanoparticle catalyst. The electrochemical performance of the SFMNi ceramic anode is greatly enhanced by the in situ exsolved Fe–Ni alloy nanoparticle catalysts that are homogeneously distributed on the ceramic backbone surface. The maximum power densities of the La_0.8Sr_0.2Ga_0.8Mg_0.2O_3−δ electrolyte supported a single cell with SFMNi as the anode reached 590, 793, and 960 mW cm^–2 in wet H₂ at 750, 800, and 850 °C, respectively. The Sr₂FeMo_0.65Ni_0.35O_6−δ anode also shows excellent structural stability and good coking resistance in wet CH₄. The prepared SFMNi material is a promising high-performance anode for solid oxide fuel cells.