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Polybenzimidazoles (PBIs) have been investigated extensively for a number of applications such as films, fibers, blown and syntactic foams, moldings, and so on. PBI composites provide useful engineering strengths to higher temperature composites than other high temperature composites such as the polyimides. In this article, particular attention is given to one member of this family of polymers that is the poly[2′,2‐(m‐phenylene) ‐5,5′‐bibenzimidazole]. In particular, some properties of PBI composites and some processes to obtain high temperature composites such as autoclave processing are presented. To word the conclusion of the article, some examples of applications such as PBI–carbon fiber missile fin or optical coating for use in the space are presented.