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China has the rich bamboo resource, moreover, the species and yield of bamboo both are the first in the world. The extract of bamboo root was often used to cure some intractable diseases in the countryside of China, but the components of bamboo root extract is still unresolved. In order to expedite medicinal application of bamboo root, and to provide further scientific foundation for its top value-added development, pyrolysis- GC/MS technology was used to identify and analyze the top value-added biomedical and bioactive components of benzene/ethanol extract of Moso bamboo root. The extract was pyrolyzed at 750 °C in helium atmosphere, and then the pyrolyzate was analyzed by online-linked GC/MS. Relative content of each component was determined by area normalization. 87 compounds representing 98.31% were identified from 105 peaks. The result showed that the pyrolyzate of benzene/ethanol extract of Moso bamboo root is rich in biomedical components, and also contains some bioactive components which can be used as top value-added materials of high-grade spice, cosmetic, food, and chemical.