Microbial infection of plants or elicitation of cell cultures initiates substantial metabolic changes directed at the induction of defence reactions. The antimicrobial phytoalexins deserve special attention because they represent one essential component of plant resistance. The great structural diversity of phytoalexins and possible cellular sites for their toxic activity are discussed. Pterocarpan phytoalexin biosynthesis in Cicer arietinum is an example of the induction of extended biosynthetic pathways, their modes of regulation and metabolic links with constitutive secondary product formation. Elicitation of plant tissues represents a technique to induce simultaneously the formation of phytoalexins and increased levels of constitutive or other secondary products that do not normally accumulate. The biological function of phytoalexins and the pathways of their degradation by pathogenic fungi are outlined. Detoxification of phytoalexins by fungi may have important consequences for the practical application of these defence compounds and for the genetic transformation of fungi and plants. Phytoalexins accumulate in plants or cell cultures only transiently, because they are readily degraded or polymerized by extracellular peroxidases.