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To the best of our knowledge, this is the first study to use liquid chromatography/multistage mass spectrometry to demonstrate the distribution of eight vitamin E homologs in plants. Many tocopherol homologs, which showed higher antioxidant activity than tocotrienol homologs, were discovered and α-tocopherol, which had the highest antioxidant activity among these homologs, was widely distributed in all plants. In addition, α-tocopherol occurred at high concentrations in the leaves of plants belonging to the sumac family, which is native to tropical regions. Furthermore, 25.9% of plants contained α-tocopherol alone, whereas the remaining 74.1% contained α-tocopherol in combination with other homologs. The detection frequency was the highest for a combination of α-tocopherol and γ-tocopherol, which is a precursor of α-tocopherol in plants. The highest number of vitamin E homologs was found in leaves, followed by stems, flowers, branches, and buds. Furthermore, tocotrienol homologs were present only in leaves. This indicates that the distribution of homologs in plants reflects the intensity of the antioxidant activity of homologs. It also suggests that the distribution of α-tocopherol in combination with γ-tocopherol is influenced by the α-tocopherol synthetic pathway in plants.