Numerous coexisting species can be observed in the open oceans. This includes the complex community of the plankton, which comprises all free floating organisms in the sea. Traditionally, nutrient limitation, competition, predation, and abiotic factors have been assumed to shape the community structure in this environment. Only in recent years has the idea arisen that chemical signals and chemical defense can influence species interactions in the plankton as well. Key players at the base of the marine food web are diatoms (unicellular algae with silicified cell walls) and their main predators, the herbivorous copepods. It was assumed that diatoms represent a generally good food source for the grazers but recent work indicates that some species use chemical defenses. Secondary metabolites, released by these algae immediately after wounding, are targeted not against the predators themselves but rather at interfering with their reproductive success. This strategy allows diatoms to reduce the grazer population, thereby influencing the marine food web. This review addresses the chemical ecology of the defensive oxylipins formed by diatoms and the question of how these metabolites can act in such a dilute environment. Aspects of biosynthesis, bioassays, and the possible implications of such a chemical defense for the plankton community structure are also discussed.