The first phytochemical investigation on the roots of Ligularia purdomii led to the isolation and identification of 18 compounds, including two eremophilane sesquiterpenoids (1 and 2), three benzofuran derivatives (3-5), a triterpenoid (6), two steroids (7 and 8), nine phenolic components (9-17), and a monofatty glyceride (18). The structural elucidation of the isolated compounds was performed by spectroscopic data and comparison with the literature. Compounds (-)-syringaresinol (11), scopoletin (13), 3,5-dimethoxy-4-hydroxy-benzaldehyde (14), and glycerol monolinoleate (18) have not been recorded in Ligularia genus previously. The chemotaxonomic significance of these isolated compounds has been summarized.