Covering: up to September 2012. Saponins are an important class of plant natural products that consist of a triterpenoid or steroidal skeleton that is glycosylated by varying numbers of sugar units attached at different positions. Steroidal saponins are usually divided into two broad structural classes, namely spirostanol and furostanol saponins. A third, previously unrecognized structural class of plant saponins, the open-chain steroidal saponins, is introduced in this review; these possess an acyclic sidechain in place of the heterocyclic ring/s present in spirostanols and furostanols. Open-chain steroidal saponins are numerous and structurally diverse, with over 150 unique representatives reported from terrestrial plants. Despite this, they have to date been largely overlooked in reviews of plant natural products. This review catalogs the structural diversity of open-chain steroidal saponins isolated from terrestrial plants and discusses aspects of their structure elucidation, biological activities, biosynthesis, and distribution in the plant kingdom. It is intended that this review will provide a point of reference for those working with open-chain steroidal saponins and result in their recognition and inclusion in future reviews of plant saponins.