Oxygen carriers (OCs) with high reactivity and stability are eagerly desired in the chemical looping process to achieve efficient oxygen transfer among different reductants. Al 2 O 3 is a widely used support in preparing Fe 2 O 3 -based OCs due to its low cost and adjustable texture. Also, diverse performances were obtained for the Fe 2 O 3 −Al 2 O 3 synthesized with different Al 2 O 3 precursors; however, how the Al 2 O 3 type influences the performance of Fe 2 O 3 -based OCs is still unclear, which confuses the choice of Al 2 O 3 in preparing the OCs. In the present work, seven types of Al 2 O 3 precursors were adopted to prepare the Fe 2 O 3 −Al 2 O 3 by mechanical mixing, then the reactivity and stability of these OCs were assessed in a chemical looping hydrogen generation process, and the way Al 2 O 3 affects the performance of OCs was analyzed via XRD, SEM, BET, TPR, and XPS analysis on the calcined Al 2 O 3 precursors and the prepared OCs. Results showed that the high reactivity of Fe 2 O 3 −Al 2 O 3 originated from the improved internal diffusion and high oxygen deficiency and adsorbed oxygen content. Furthermore, structure− activity correlation analysis implied that the microtexture plays a bigger role in the OC reactivity and stability when compared with other physical characteristics, and the Fe 2 O 3 −Al 2 O 3 OCs with high surface area and pore volume achieved nearly 100% fuel conversion, meanwhile produced a higher yield of H 2 (1.6 mmol/g Fe 2 O 3 ), and showed a stable behavior in cycling tests. Furthermore, compared to other properties of the Al 2 O 3 -supported OCs, we found that the solubility of Al 2 O 3 in Fe 2 O 3 is the dominant factor that affects the hercynite formation during the Fe 2 O 3 −Al 2 O 3 reduction process.