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Reforestation projects have gained interest over recent years due to the loss of biodiversity in tropical regions as a result of large deforestation by anthropogenic actions. However, better knowledge on the tolerance of plant species to environmental stresses is needed for reforestation success. Here, we evaluated the photoprotective and antioxidant capacity, in terms of vitamin E accumulation, of five pioneer (Platypodium elegans Vogel, Schinus terebinthifolius Raddi, Lafoensia pacari A. St.-Hil, Cecropia pachystachya Trécul. and Aegiphila sellowiana Cham.) and five non-pioneer (Myracrodruon urundeuva Allemão, Cedrela fissilis Vell., Genipa americana L., Copaifera langsdorffii Desf. and Hymenaea courbaril L.) species, in relation to the extent of lipid peroxidation in leaves. Furthermore, we examined differences between sun and shade leaves on vitamin E accumulation and the extent of lipid peroxidation. Pioneer plants showed on average 33% higher malondialdehyde levels, an indicator of lipid peroxidation, than non-pioneer species, but no significant differences in vitamin E contents. In contrast, a marked interspecific variation was observed in the levels of α-tocopherol and its precursor, γ-tocopherol. Natural variation revealed interesting relationships between vitamin E levels and the extent of lipid peroxidation in leaves. The pioneer species, P. elegans, did not accumulate α-tocopherol and displayed the highest levels of malondialdehyde. Sun and shade leaves accumulated vitamin E levels to a similar extent, except for the pioneer L. pacari and the non-pioneer C. langsdorffii, the former accumulating more α-tocopherol in sun leaves and the latter in shade leaves. We conclude that interspecific variation is higher than both leaf type and successional-group variation in terms of vitamin E accumulation and the extent of lipid peroxidation, and that vitamin E levels, particularly those of α-tocopherol, negatively correlate with the extent of lipid peroxidation, thus supporting a photoprotective and antioxidant function for vitamin E in plants growing in tropical environments.