Lipid oxidation in milk and dairy products is a chain reaction initiated by formation of free radicals (Richardson & Korycka-Dahl, 1983). Thanks to intensive studies on both model systems and actual food, the autocatalytic process, including the formation of secondary lipid oxidation products from the lipid hydroperoxides formed initially, is fairly well understood. However, actually predicting the rate at which the first free radicals leading to spontaneous oxidation are formed in milk from different cows awaits the development of new analytical methods with higher specificity and sensitivity (Nicholson, 1993; Barrefors et al. 1995). Such methods would also be valuable for predicting the stability and shelf life of dried dairy products, which are determined by oxidative phenomena. Electron spin resonance (ESR) spectrometry has the potential for detecting the early events in lipid oxidation, as it is the only spectrometric method that will directly detect the unpaired electron characteristic of the free radical and it is, moreover, a highly sensitive method (Brudvig, 1995). ESR spectrometry has recently been shown to provide quantitative information on the level of free radicals in milk powder that correlates with the level of secondary oxidation products developed upon reconstitution and that also correlates with subsequent sensory evaluation (Nielsen et al. 1997; Stapelfeldt et al. 1997a, b, c). However, in order to explore further the potential of this method for raw milk, it was considered valuable to measure the tendency of milk to form free radicals in relation to its level of α-tocopherol, the most important lipophilic chain-breaking antioxidant (cf. Kamal-Eldin & Appelqvist, 1996).