Chemical looping hydrogen (CLH) production, or hydrogen production combined with CO2 capture, is becoming an emerging alternative technology that has attracted much attention. Iron-based oxygen carriers were most widely used in CLH. In this study, bi-active component composite metal oxides with Cu-doped Fe2O3/Al2O3 were synthesized. The oxygen carriers were characterized using different methods such as X-ray diffraction (XRD), scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET), and their redox and cycle properties in the CLH process were investigated. The results showed that copper doping enhanced the activities of iron-based oxygen carriers, but excessive copper would reduce their reactivity due to melting and agglomeration. Hydrogen temperature-programmed reduction (H-2-TPR) analysis, fixed-bed experiments, and density functional theory (DFT) calculations all confirmed that Cu promoted the deep reduction of Fe2O3. Among them, the oxygen carrier doped with 1 wt % CuO was the most suitable material for CLH, where H-2 yield was the highest and sustained in a high and stable level in multiple redox cycles.