Dry reforming of methane simultaneously achieves several sustainability goals: valorizing methane-activating carbon dioxide while producing syngas. The catalyst has an enormous influence on the process viability by controlling activity, selectivity, and stability. A catalyst with uniform-sized Ni-Fe alloy nanoparticles anchored into PrBaMn1.6Ni0.3Fe0.1O5+δ double-layered perovskite is assembled via a facile one-step reduction strategy. Our method attains more exsolved Ni nanoparticles (94 %) than the common conditions. The exsolved Ni0.15Fe0.05 catalyst shows exceptional stability in 260 h tests at 800 °C, with one of the slowest coke formation rates compared with the state-of-the-art catalysts. Besides, no deactivation was observed during 40 h operation at more demanding and coking conditions (14 bar) where this process is more likely to operate industrially. Via experimental characterizations and computational calculations, the stability of the robust exsolved Ni-Fe catalyst is demonstrated by its unique balance of adsorbed species, which inhibits coking.