Sorption-enhanced water-gas shift (SEWGS) is a promising technology for precombustion CO2 capture with high energy efficiency. Hydrotalcite-based adsorbents were studied as possible solid sorbents for pressure swing adsorption under SEWGS conditions. They show high thermal and mechanical stability with sufficiently high cyclic working capacity and fast adsorption kinetics. The regenerations step (desorption of CO2 by feeding steam to the adsorbent) is slower and limits the cyclic working capacity of the adsorbent. It was found that a higher operating temperature is beneficial because of enhanced desorption kinetics. Steam induces the desorption of a second adsorption site available for CO2 which cannot be desorbed with N2. Different adsorption sites are present on the hydrotalcite material. On the basis of a dedicated set of high-pressure breakthrough experiments an adsorption isotherm has been developed which describes the interaction of CO2 and H2O with the hydrotalcite-based adsorbent over the relevant range of partial pressures. Based on the isotherm and a linear driving force approximation for intraparticle mass transfer, a reactor model has been constructed for the simulation and optimization of SEWGS cycles. A parameter study of SEWGS cycles shows that the high-pressure rinse steam improves the CO2 product purity, while the low-pressure steam purge mainly serves to improve the CO2 capture ratio. Finally, a comparative analysis of the required work of precombustion separation of CO2 and H2 shows that SEWGS outperforms conventional technologies for hydrogen-carbon dioxide separation, partly because of its inherently high CO2 capture ratio.