In production of electricity from coal, integrated gasification combined cycle plants typically operate with conventional packed bed reactors for the water-gas shift reaction, and a Selexol process for carbon dioxide removal. Implementation of membrane reactors in place of these two process units provides advantages such as increased carbon monoxide conversion, facilitated CO₂ removal/sequestration and process intensification. Proposed H₂-selective membranes for these reactors are typically of palladium alloy or ceramic due to their outstanding gas separation properties; however, on an industrial scale, the cost of such materials may become exorbitant. High-performance polymeric membranes, such as polybenzimidazoles (PBIs), present themselves as low-cost alternatives with gas separation properties suitable for use in such membrane reactors, given their significant thermal and chemical stability. In this work, the performance of a class of high-performance polymeric membranes is assessed for use in integrated gasification combined cycle (IGCC) units operated with carbon capture, subject to constraints on equipment and process streams. Several systems are considered for use with the polymeric membranes, including membrane reactors and permeative stage reactors. Based upon models developed for each configuration, constrained optimization problems are formulated which seek to more efficiently employ membrane surface area. From the optimization results, the limiting membrane parameter for achieving all carbon capture and H₂ production specifications for water⁻gas shift reactor applications is determined to be the selectivity, α H 2 / C O 2, and thus a minimum value of this parameter which satisfies all the constraints is identified for each analyzed configuration. For a CO₂ capture value of 90%, this value is found to be α = 61 for the membrane reactor and the 3-stage permeative stage reactor and α = 62 for the 2-stage permeative stage reactor. The proposed systems approach has the potential to be employed to identify performance limitations associated with membrane materials to guide the development of future polymeric and other advanced materials with desired membrane characteristics for energy and environmental applications.