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This chapter discusses the importance of vitamin E in human milk, in the initial periods of lactation. Nutritional and deficiency aspects will be covered, since maternal milk must provide adequate support in order to ensure the formation of reserves and strengthen the newborn's defenses against the effects of vitamin E deficiency and oxygen toxicity. The role of maternal milk as an indicator of nutritional status will also be discussed as well as a review of several studies that investigated vitamin E in maternal milk. Finally, we will present a number of factors that can affect alpha-tocopherol concentration in human milk, such as nutritional status, maternal diet, maternal age, number of deliveries and nutrient-nutrient interaction.