This is a complete (Fiscal Years 2000-2006) collection of the Idaho National Laboratory's (INL) research and development contributions to the project, CO2 Separation Using Thermally Optimized Membranes. The INL scientific contribution to the project has varied due to the fluctuations in funding from year to year. The focus of the project was polybenzimidazole (PBI) membranes and developing PBI compounds (both substitution and blends) that provide good film formation and gas separation membranes. The underlying problem with PBI is its poor solubility in common solvents. Typically, PBI is dissolved in aggressive solvents, like N,N-dimethylacetamide (DMAc) and N methylpyrrolidone (NMP). The INL FY-03 research was directed toward making soluble N-substituted PBI polymers, where INL was very successful. Many different types of modified PBI polymers were synthesized; however, film formation proved to be a big problem with both unsubstituted and N-substituted PBIs. Therefore, INL researchers directed their attention to using plasticizers or additives to make the membranes more stable and workable. During the course of these studies, other high-performance polymers (like polyamides and polyimides) were found to be better materials, which could be used either by themselves or blends with PBI. These alternative high-performance polymers provided the best pathway forward for soluble high-temperature polymers with good stable film formation properties. At present, the VTEC polyimides (product of RBI, Inc.) are the best film formers that exhibit high-temperature resistance. INL's gas testing results show VTEC polyimides have very good gas selectivities for both H2/CO2 and CO2/CH4.