The antioxidant effects of vitamin E may protect low density lipoproteins from peroxidation and thus inhibit the development of arteriosclerosis. Inverse associations between vitamin E levels and coronary heart disease have been reported from cross-sectional and ecologic studies. In the population-based MONICA Augsburg cohort (2023 men, 1999 women, age 25–64 years at baseline in 1984, 93% of whom were reexamined in 1987/1988) we investigated the relationship between serum vitamin E concentrations and the risk of subsequent myocardial infarction (MI). Between 1984 and 1991, 46 cases of fatal and non-fatal myocardial infarction from this cohort were recruited for a nested case-control study. Four controls were sampled from the cohort for each case of MI with matching for age, sex, and total cholesterol. There were no marked differences between cases and their matched controls in the means of vitamin E concentrations (33.9 μmol/l vs. 32.8 μmol/l, P = 0.37) or in the mean vitamin E/total cholesterol ratios (4.89 μmol/mmol vs. 4.82 μmol/mmol, P = 0.75). The covariate adjusted relative risk (RR) for fatal plus non-fatal MI in the lowest tertile of vitamin E relative to the upper two tertiles was 0.72 (90% confidence interval: 0.33–1.57). Likewise, for the lowest tertile of the ratio (vitamin E/total cholesterol) the RR was 0.81 (0.42–1.56). The association was not modified by history of previous coronary heart disease, fatality of MI, temporal distance of MI onset from vitamin E determinations, or season. Although the limited statistical power of this study has to be considered, risk estimates appeared too low to be compatible with a substantial protective effect of vitamin E levels. We conclude, therefore, that serum vitamin E concentrations were not associated with the myocardial infarction risk and suggest that this is probably due to the high average levels of vitamin E in our study population.