The Smilax species, widely distributed in tropical region of the world and the warm areas of East Asia and North America, are extensively used as folk medicine to treat inflammatory disorders. Chemical investigation on Smilax species showed they are rich sources of steroidal saponins with diversified structure types, including spirostane, isospirostane, furostane, pregnane, and cholestane. This review mainly summarizes the steroidal saponins (1–104) reported from the genus Smilax between 1967 and 2016, and their biological activities. The relationship between structures of steroidal saponins and related biological activities were briefly discussed.Graphical Abstract