Catalysis- and sorption-enhanced biomass gasification is a promising route to high-purity hydrogen (H(2)); however, most CaO-based sorbents for CO(2) capture have poor surface area and mechanical properties, lose carrying capacity over multiple uses, and have insufficient porosity to accommodate extra catalyst sites. We aimed to develop a high-surface-area CaO-SiO(2) framework onto which catalysts could be grafted. The best CaO-SiO(2) sorbent (n(Ca)/n(Si) = 2:1) maintained a CaO conversion of 65% even after 50 carbonation-decarbonation cycles, better than commercial micrometer-sized CaO or tailored CaO, because of stabilization via Ca-O-Si interactions and an ordered porous structure. Bimetallic catalyst grains (Ni/Co alloy, <20 nm) could be evenly loaded onto this structure by impregnation. The resulting bifunctional complex produced H(2) at nearly the same rate as a mixture of catalyst and commercial CaO while using less total sorbent/catalyst. Furthermore, this complex was much more durable due to its higher coking resistance and stable structure. After 25 carbonation-decarbonation cycles, the new catalyst-sorbent complex enhanced the H(2) yield from cellulose far more than a mixture of catalyst and commercial CaO did following the same treatment.