Peroxidation of lipids in membranes and lipoproteins proceeds through the classical free radical sequence encompassing initiation, propagation, and termination phases which are expressed by a lag phase in which little oxidation occurs, followed by a rapid increase in autocatalysis by chain-propagating intermediates and, finally, a decrease in the rate of oxidation. The lag phase is lengthened by preventive or chain-breaking antioxidants, which scavenge the initiation reaction or intercept the chain-carrying species. Hence, the lag phase in lipid peroxidation processes reflects the antioxidant status of membranes and lipoproteins and, as a corollary, their resistance to oxidation. A large number of lipid peroxidation studies with different membranes attest to the complex free radical network underlying this process. The type of initiator and the steady-state level of oxygen are important factors that affect differently the rates of the individual steps of peroxidation. Equally complex are the factors that influence the lag phase preceding the oxidation of LDL. Lipid peroxyl radicals play a key role in the dynamics of lipid peroxidation: on the one hand, the lag phase is best defined for chain-breaking compounds able to reduce peroxyl radicals; on the other hand, the overall time course of lipid peroxidation is largely influenced by the rate constants for propagation reactions and termination involving peroxyl radical recombination.