Sterically hindered amines (2,2,6,6-tetramethyl-substituted piperidines) are easily oxidized (i) by electron transfer to parent cations in n-butyl chloride solution, (ii) by the sulfate radical anion in aqueous solution, and (iii) by sensitized electron transfer to carbonyl triplets. In nonpolar surroundings in the nanosecond time range, the radical cations of the tertiary piperidines have been directly observed by optical spectroscopy to exhibit absorption maxima below lambda = 300 nm and; around 550 nm. Subsequently, they deprotonate to alpha-alkylamine radicals, which are also the first observable products of oxidation with sulfate radical anions in water. In the case of secondary piperidines, the amine radical cations deprotonate to aminyl radicals in times < 10 ns. The triplet-sensitized electron transfer to the benzophenone as well as cyclohexanone triplet results in amine-derived and ketyl-type radicals formed at a nearly diffusion-controlled rate, which suggests an electron- and subsequent proton-transfer mechanism. In the presence. of oxygen, the amine-derived radicals are oxidized to nitroxyl radicals by different pathways for secondary and tertiary piperidines. For the reaction of the nitroxyl radicals with other radicals, rate constants are found to be quite similar (about 5 x 10(8) M-1 s(-1)) for several alkyl radicals and for the tert-butyloxyl radical and less than 10(5) M-1 s(-1) for alkylperoxyl radicals. Because of the minor importance of radical reactions with the sterically hindered amines (HALS), the antioxidant effect of these compounds ought to be explained by oxidation, primarily via cationic and subsequently radical intermediates to the persistent nitroxyl radicals, which scavenge other radicals very efficiently.