By employing metal oxides as oxygen carriers, chemical looping demonstrates its effectiveness in transferring oxygen between reduction and oxidation environments to partially oxidize fuels into syngas and convert CO₂ into CO. Generally, NiFe₂O₄ oxygen carriers have demonstrated remarkable efficiency in chemical looping CO₂ conversion. Nevertheless, the intricate process of atomic migration and evolution within the internal structure of bimetallic oxygen carriers during continuous high‐temperature redox cycling remains unclear. Consequently, the lack of a fundamental understanding of the complex ionic migration and oxygen transfer associated with energy conversion processes hampers the design of high‐performance oxygen carriers. Thus, in this study, we employed in situ characterization techniques and theoretical calculations to investigate the ion migration behavior and structural evolution in the bulk of NiFe₂O₄ oxygen carriers during H₂ reduction and CO₂/lab air oxidation cycles. We discovered that during the H₂ reduction step, lattice oxygen rapidly migrates to vacancy layers to replenish consumed active oxygen species, while Ni leaches from the material and migrates to the surface. During the CO₂ splitting step, Ni migrates toward the core of the bimetallic oxygen carrier, forming Fe–Ni alloys. During the air oxidation step, Fe–Ni migrates outward, creating a hollow structure owing to the Kirkendall effect triggered by the swift transfer of lattice oxygen. The metal atom migration paths depend on the oxygen transfer rates. These discoveries highlight the significance of regulating the release–recovery rate of lattice oxygen to uphold the structures and reactivity of oxygen carriers. This work offers a comprehensive understanding of the oxidation/reduction‐driven atomic interdiffusion behavior of bimetallic oxygen carriers.