Abstract:Streptococcus pneumoniae causes serious diseases such as pneumoniae and meningitis in humans. Capsular polysaccharides (CPSs) surrounding bacteria are not only key virulence factors but also major antigens. Therefore, CPSs have been prepared into polysaccharide vaccines and polysaccharide conjugate vaccines, which have greatly reduced the infection of pneumococci. CPSs are formed by polymerization of oligosaccharide repeating units which generally have 2−8 monosaccharides. CPSs present complex structures with diverse antigenic epitopes, being the basis of bacterial serotyping. Currently, 107 serotypes of S. pneumoniae have been identified. Each serotype has a unique CPS structure, a stable genetic basis, and specific serological characteristics. The diversity and constant changes of CPS structures explain the difficulty in the eradication of pneumococci. This review summarizes the known chemical structures of 95 CPSs and discusses the genetic basis, biosynthesis mechanism, and purification methods of CPSs. This review aims to enrich the knowledge about CPS diversity and provide a reference for probing into the functions and evolution of CPSs as well as for preparing polysaccharide vaccines.