Chemical looping dry reforming (CLDR) provides a novel route to directly produce F-T ready syngas with suitable H2/CO ratio (~2.0) from methane in combined with CO2 utilization, which is highly dependent on the design and elaboration of high efficient oxygen carriers (OCs). Iron oxides are promising OCs for chemical looping technology, but high potential to carbon deposition over metallic Fe0 greatly limits the improvement of methane-to-syngas selectivity via. Herein, we found that the in-situ formed CeFexAl1-xO3 over ceria-hexaaluminate as “oxygen pool” could greatly improve carbon resistance even with presence of Fe0. Formation of CeFexAl1-xO3 only proceeds in ceria-hexaaluminate composite while not occurs in CeO2-Fe2O3-Al2O3, which was probably originated from the strong interaction between CeO2 and the adjacent Fe and Al ions in BaFe3Al9O19 hexaaluminate structure. CeFexAl1-xO3 with outstanding oxygen ion conduction capacity was in close contact with metallic Fe0 exsoluted from Fe-hexaaluminate in a unique CeFexAl1-xO3/Fe0/hexaaluminate sandwich-like structure, which provided a convenient pathway for CeFexAl1-xO3 as “oxygen pool” to supply sufficient oxygen for in-time oxidation of carbon over adjacent Fe0. Consequently, the recycled ceria-hexaaluminate displayed both outstanding carbon resistance and high CH4 conversion (~90%) with enhanced syngas yield that 105% and 72% higher than CeO2-Fe2O3-Al2O3 oxide and Fe-hexaaluminate, respectively.