Polyunsaturated fatty acids (PUFAs) are important constituents in all organisms. They fulfil many functions, ranging from modulating the structure of membranes to acting as precursors of physiologically important molecules, such as the prostaglandins, which for a long time were the most prominent cyclic PUFA metabolites. However, since the beginning of the 1990s a large variety of cyclic metabolites have been discovered that form under autoxidative conditions in vivo to a much larger extent than do prostaglandins. These compounds--isoprostanes, neuroprostanes, phytoprostanes, and isofurans--proved subsequently to be ubiquitous in nature. They display a wide range of biological activities, and isoprostanes have become the currently most reliable indicators of oxidative stress in humans. In a relatively short time, the structural variety, properties, and applications of the autoxidatively formed cyclic PUFA derivatives have been uncovered.