Amphibians occupy a wide range of habitat types from arid deserts to deep freshwater lakes; they may spend most of their life underground or high in cloud forest canopy. Some are found north of the Arctic Circle and can tolerate freezing conditions, while others have evolved a range of adaptations to avoid desiccation in some of the hotter areas of the world. The skin plays key roles in the everyday survival of amphibians and their ability to exploit a wide range of habitats and ecological conditions. The normal functions of the skin are surveyed and Eisner's biorational approach to chemical prospecting – seeking clues from an animal's behaviour and its interactions with its environment to reveal the presence of chemical compounds with potential medical or veterinary applications – is applied to amphibians. The biology and natural history of amphibian skin, its glands and their secretions are briefly reviewed. Four categories of compounds are found in the granular or poison glands, these are: biogenic amines, bufodienolides (bufogenins), alkaloids and steroids, peptides and proteins. Toads, particularly members of the genus Bufo, are identified as a particularly convenient and useful source of granular gland secretions. The potential medical-pharmaceutical significance of products derived from amphibian skin secretions is discussed. The need for a humane approach to this work is noted.