The chemical looping concept provided a novel way to achieve carbon separation during the production of energy or substances. In this work, hydrogen generation with inherent CO₂ capture in single packed bed reactor via this concept was discussed. Two oxygen carriers, Fe₂O₃ 60 wt.% and Fe₂O₃ 55 wt.%/CuO 5 wt.% supported by Al₂O₃, were made by ball milling method. First, according to the characteristics of the reduction breakthrough curve, a strict fuel supply strategy was selected to achieve simultaneous CO₂ capture and H₂ production. Then, in the long term tests using CO as fuel, it was proved that CuO addition improved hydrogen generation with the maximum intensity of 3700 μmol H₂·g⁻¹ Fe₂O₃ compared with Fe-Al of 2300 μmol H₂·g⁻¹ Fe₂O₃. The overall CO₂ capture efficiency remained 98%–98.8% over 100 cycles. Moreover, the reactivity of deactivated materials was recovered nearly like that of fresh ones by sintering treatment. Finally, two kinds of complex gases consist of CO, H₂, CH₄ and CO₂ were utilized as fuels to test the feasibility. The results showed all components could be completely converted by Fe-Cu-Al in the reduction stage. The intensity of hydrogen production and the overall CO₂ capture efficiency were in the range of 2000–2400 μmol H₂·g⁻¹ Fe₂O₃ and 89%–95%, respectively.