Chemical looping hydrogen generation (CLHG) offers a promising solution for producing H2 from industrial off-gas, such as blast furnace gas. However, increasing H2 production capacity of the oxygen carrier (OC) at moderate temperature remains a significant challenge. In this study, a novel Cu-Fe-based OC is tailored for moderate-temperature CLHG from blast furnace gas. The results demonstrates that the tailored OC exhibits a superior H2 production capacity of 12.99 mmol·g−1 at 550 °C, which is 6.5 times higher than that of Fe2O3 at the same temperature. The addition of Cu leads to the formation of oxygen defects, which facilitate the migration of lattice oxygen, thereby the activity of the OC is enhanced. Furthermore, cyclical experiments demonstrates that O2-assisted regeneration strategy can effectively suppress the segregation of Cu during the cycling process, and the tailored OC shows good stability during 10 redox cycles. No additional separation process was required and the purity of the hydrogen was higher than 99%. The findings here open a new avenue for efficient CLHG from industrial off-gas at moderate operation temperature.