Coumarins are a class of naturally occurring compounds found in various plants, fungi, and microorganisms, each with a unique chemical profile. These compounds exhibit a broad range of bioactivities, including antithrombotic, anti-inflammatory, antioxidant, antimicrobial, antiviral, anticancer, and neuroprotective properties. The effective extraction of coumarins, facilitated by methods such as maceration and microwave-assisted extraction, is integral to unlocking their potential across various applications. Nevertheless, safety and toxicology considerations assume paramount importance, particularly in pharmaceuticals, cosmetics, and food additives. While moderate dietary consumption of coumarin-rich foods is generally safe, excessive intake, whether through foods or supplements, raises concerns linked to hepatotoxicity and photosensitivity. Notably, specific coumarin derivatives, including the widely used anticoagulant warfarin, necessitate precise dosing and vigilant monitoring to mitigate the risk of bleeding complications. In conclusion, the versatile biological activities of coumarins underscore their significance; yet, their safety and toxicity profiles are contingent on multiple factors, encompassing compound type, dosage, and individual susceptibility. This review provides a holistic understanding of coumarins, encompassing their natural origins, biosynthesis, bioactivity spectrum, extraction techniques, and insights into safety, and toxicology.