Steroidal alkaloids are derived from the steroid skeleton with one or two nitrogen atoms. They are widely distributed in tropical and subtropical regions and possess a range of biological activities. The structures of steroidal alkaloids are comparable to those of anabolic steroids, steroidal hormones, and corticosteroids, making them a valuable source for drug discovery. Taxonomically, steroidal alkaloids are limited in distribution to certain plant families, predominantly the Apocynaceae, Buxaceae, Solanaceae, and Liliaceae. This review highlights the steroidal alkaloids from the Apocynaceae family and their biological activities. The articles published from 1919 to 2021 were included in this review. A total of 163 steroidal alkaloids and 12 biological activities were reported from plant species belonging to the Apocynaceae family in this period. Of the 410 genera in the Apocynaceae, only 10 contain steroidal alkaloids. Although some alkaloids from the Apocynaceae family were also reported in the Buxaceae family, especially tetracyclic triterpenes with a pregnane side chain, most steroidal alkaloids can only be found in several genera of the Apocynaceae family.