A mesoporous sorption complex catalyst was prepared by pore-forming modification and evaluated by the COz reactive sorption enhanced reforming (ReSER) process, which is used to produce hydrogen from methane. Three samples of polyethylene glycol (PEG) with molecular weights between 2000 and 20 000 were added as templates into a mixed slurry to create catalysts with different pore properties by further formation and calcination. The pore characteristics determined by Brunauer- Emmett-Teller (BET) analysis showed that one of the mesoporous catalysts, named M-NiAICa-6000, had a pore size of 9.2 nm and a surface area of 70.52 m2/g and the CO2 sorption capacity of this catalyst was 44% higher than that of the catalyst without the PEG 6000 modification. The catalyst was evaluated in the ReSER process in a fixed-bed reactor system at 0.1 MPa and 600 C with an H20/CH4 molar ratio of 4. An H2 concentration of 94.2% and a CH4 conversion of 86.0% were obtained at a carbon space velocity of 1700 h 1 while CO2 was hardly detected.