<p>Biflavonoids from the Thymelaeaceae family are gaining increasing attention due to their diverse pharmacological activities and considerable potential as therapeutic agents. Biflavonoids derived from genera such as <i>Stellera</i>, <i>Wikstroemia</i>, and <i>Daphne</i> have emerged as focal points in natural product-based drug discovery. Previous studies have documented the ethnopharmacological applications of Thymelaeaceae species while providing analyses of their phytochemical constituents. However, systematic reviews critically evaluating the structural diversity, pharmacological activities, and structure–activity relationships of Thymelaeaceae-derived biflavonoids remain scarce. Therefore, the main objective of this review is to summarize recent research reports on biflavonoids isolated from Thymelaeaceae plants up to the present, including their structural features, classification based on linkage patterns, and pharmacological activities, with particular emphasis on anticancer, antiviral, and anti-inflammatory effects. Furthermore, this article discusses structure–activity relationships of representative biflavonoids, highlighting how specific structural features—such as C-3/C-3″ linkages, methoxy substitution, and stereochemical configuration—critically influence their bioactivity. By identifying current research gaps and proposing future directions, this review aims to provide a comprehensive reference for the continued development of Thymelaeaceae biflavonoids as potential drug candidates.</p> Graphical abstract <p></p>