Stevioside, an ent-kaurene type of diterpenoid glycoside, is a natural sweetener extracted from leaves of Stevia rebaudiana (Bertoni) Bertoni. Stevioside and a few related compounds are regarded as the most common active principles of the plant. Such phytochemicals have not only been established as non-caloric sweeteners, but reported to exhibit some other pharmacological activities also. In this article, natural distribution of stevioside and related compounds, their structural features, plausible biosynthetic pathways along with an insight into the structure–sweetness relationship are presented. Besides, the pharmacokinetics, wide-range of pharmacological potentials, safety evaluation and clinical trials of these ent-kaurene glycosides are revisited.