<p>Benzocoumarins, a π-extended subclass of coumarins, have garnered growing interest due to their unique structural architecture and remarkable spectrum of biological activities. These fused aromatic heterocycles, also known as benzochromenones, feature a benzene ring fused at various positions of the coumarin scaffold, enhancing their π-conjugation and expanding their pharmacological potential. Naturally occurring and synthetically accessible, benzocoumarins have been isolated from diverse biological sources including fungi, lichens, and higher plants. They exhibit a broad array of pharmacological properties, such as anticancer, antioxidant, antidiabetic, antimicrobial, antidyslipidemic, and immunomodulatory effects. These bioactivities are often closely linked to their substitution patterns and ring fusion positions. The synthesis of benzocoumarins has evolved significantly, employing classical methods such as Pechmann and Knoevenagel condensations, as well as modern approaches including metal-catalyzed cyclization, ring-closing metathesis, and one-pot multi-step reactions. Recent advances have focused on eco-friendly and high-yielding protocols, highlighting the importance of green chemistry in heterocyclic synthesis. This review presents a detailed classification of benzocoumarins based on their fusion patterns—namely benzo[<i>c</i>]-, benzo[f]-, benzo[<i>g</i>]-, and benzo[<i>h</i>]coumarins—along with an extensive overview of their synthetic routes and structure–activity relationships. Furthermore, it sheds light on their therapeutic potential as drug leads in oncology, metabolic disorders, infectious diseases, and inflammation. By consolidating the current state of knowledge, this work underscores the relevance of benzocoumarins as promising scaffolds in medicinal chemistry and encourages further exploration into their design, synthesis, and pharmacological evaluation.</p> Graphical abstract <p></p>