As the demand for eco-friendly energy increases to overcome the energy shortage and environmental pollution crisis, hydrogen economy has been proposed as a potential solution. Accordingly, an economical and efficient hydrogen production is considered to be an essential industrial process. Research on applying hydrogen separation membranes for H2/CO2 separation to the production of highly concentrated hydrogen by purifying H2 and capturing CO2 simultaneously from synthetic gas produced by gasification is in progress nowadays. In high temperature environments, the membrane separation process using glassy polymeric membrane with H2 selectivity has the potential for CO2 capture performance, and is an energy and cost effective system since polybenzimicazole (PBI)-based separators show excellent chemical and mechanical stability under high-temperature operation conditions. Thus, the development of high-performance PBI hydrogen separators has been rapidly progressing in recent years. This overview focuses on the recent developments of PBI-based membranes including structure modified, cross-linked, blended and carbonized membranes for applications to the industrial hydrogen separation process.