The selection of metal oxides and supports to improve catalytic activity and stability of oxygen carriers (OCs) is crucial for chemical looping steam reforming (CLSR) to hydrogen production. In this study, the Ni-based MCM-41 and SBA-15 OCs with and without CeO₂ promoter were prepared by direct synthesis and impregnation methods. The BET, XRD, TEM, ICP-AES, H₂-TPR and DSC-TGA were used to analyze the synthesized OCs. Hydrogen production by CLSR using biodiesel byproduct glycerol was studied in a fixed-bed reactor with fuel and air stages. The DSC-TGA experiments were carried out to determine the thermal decomposition of biodiesel byproduct glycerol and the results indicated the exothermic and/or endothermic reactions as a result of secondary reactions and, the main degradation with the mass loss of 85.5 wt% occurred in the stages of 150-500 °C. The mesoporous OCs presented high specific surface area, large pore volume, and uniform pore size. It was found that the NiO and CeO₂ in the mesoporous OCs were first reduced by fuels and the reduced OCs was responsible of steam reforming and water gas shift (WGS) to hydrogen production, and hydrogen selectivity was up to 90% using CeNiO/SBA-15. The mesoporous OCs with Ce promoter greatly shortened ‘dead time’ (the reduce time of OCs), and effectively suppressed carbon deposited on OCs. High loading of NiO and CeO₂ on SBA-15 improved oxygen transfer and achieved excellent cyclic stability., These findings provide the fundamental understanding and principle of design on the conventional Ni-based OCs with room for further developments in chemical looping process.