The sorption-enhanced steam methane reforming (SE-SMR) reaction using a mixture of a Ni-hydrotalcite-derived catalyst synthesized via coprecipitation and Ca-based sorbents synthesized by the sol-gel technique was investigated. The materials were characterized by X-ray diffraction, N-2 physisorption, and scanning electron microscopy. Under SE-SMR conditions, the mole fraction of hydrogen in the effluent stream was 0.99 in the pre-breakthrough stage (dry and without inert component), thus reaching thermodynamic equilibrium. The stability of the synthetic Ca-based material was attributed to the formation of a finely and homogeneously dispersed high Tammann temperature support which stabilized its nanostructured morphology.