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Olive oil production generates large quantities of margine, a polluting by-product. The olive oil industry faces two major challenges: reducing the environmental impact of margine, and valorizing its bioactive compounds, notably polyphenols. This review explores the phytochemical composition of margine, polyphenol extraction methods and their pharmaceutical applications. Extraction can be performed by simple (liquid-liquid extraction) or advanced (membrane extraction, combined methods) techniques, offering variable yields. The composition of margine, including polyphenols, polysaccharides, lipids, proteins and mineral salts, varies according to olive variety, climate and region. Polyphenolic extracts have anti-inflammatory, antimicrobial and antioxidant properties. They can be used in cosmetics, nutrition or in the treatment of diseases such as cancer, diabetes or hypercholesterolemia. Further studies are needed to ensure their industrialization and use in humans.