An energy scenario, mainly based on renewables, requires efficient and flexible Power-to-X (P2X) storage technologies, including the methanation of CO₂. As active Ni⁰ surface sites of monometallic nickel-based catalysts are prone to surface oxidation under hydrogen-deficient conditions, we investigated iron as “protective” dopant. A combined operando X-ray absorption spectroscopy and X-ray diffraction setup with quantitative on-line product analysis was used to unravel the structure of Ni and Fe in an alloyed Ni-Fe/Al₂O₃ catalyst during dynamically driven methanation of CO₂. We observed that Fe protects Ni from oxidation and is itself more dynamic in the oxidation and reduction process. Hence, such “sacrificial” or“protective” dopants added in order to preserve the catalytic activity under dynamic reaction conditions may not only be of high relevance with respect to fine-tuning of catalysts for future industrial P2X applications but certainly also of general interest.