Crocus sativus L. is largely cultivated because it is the source of saffron, a well-appreciated and valued spice, not only for its culinary use but also because of its significant biological activities. Stigmas are the main product obtained from flowers, but in addition, tepals, largely considered a waste product, represent a big source of flavonoids and anthocyanins. This study aimed to delve into the phytochemical composition of saffron tepals and investigate whether the composition was influenced by the extraction technique while investigating the main analytical techniques most suitable for the characterization of tepal extracts. The research focuses on flavonoids, a class of secondary metabolites, and their health benefits, including antioxidant, anti-inflammatory, and anticancer properties. Flavonoids occur as aglycones and glycosides and are classified into various classes, such as flavones, flavonols, and flavanones. The most abundant flavonoids in tepals are kaempferol glycosides, followed by quercetin and isorhamnetin glycosides. Overall, this review provides valuable insights into the potential uses of tepals as a source of bioactive compounds and their applications in various fields, promoting a circular and sustainable economy in saffron cultivation and processing.