Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Pyrrolizidine alkaloids (PAs), mainly those with a 1,2-double bond in the necine base moiety (=1,2-dehydropyrrolizidines), constitute a class of well studied compounds with respect to their flux through different trophic levels. Plants belonging to various clades (e.g. Echiteae, Eupatorieae and Senecioneae, Boraginaceae, and Crotalarieae) biosynthesize PAs as N-oxides, generally in the roots, and transport them through the phloem to stems, leaves, and reproductive structures, where they act as potent deterrents against non-specialist herbivores. On the other hand, PA specialist herbivores (mainly arctiid moths, danaine and ithomiine butterflies, and some leaf beetles) have become able to overcome this chemical barrier, and to sequester these alkaloids from their larval host plants or from sources visited by adults, such as flowers and dead or withered plants. Specialists use PAs for their own benefit as chemical defence against a vast array of predators (e. g. ants, lacewings, spiders, lizards, birds, and mammals), but some predators are able to feed on PA-insects, by avoiding or physiologically overcoming PAs present in tissues of the ingested prey. Parasitoids may be affected by PAs, depending on their degree of specialization in relation to PA-insects. Arctiidae, Danainae and Ithomiinae also use PAs as precursors of sexual pheromones. The effects of PAs on trophic interactions have been intensely studied over the last four decades, but some open questions remain, and are discussed, such as the underlying mechanisms that lead to PA diversification, activity of different PA structures, synergism among PAs and other so-called defensive substances in PA-plants, and the ability to overcome this chemical barrier by predators and parasitoids.101SI8398Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)CNPq [304473/2009-0]