The phytochemical study of the whole plants of Ligularia sagitta led to the isolation of 26 compounds, including a new eremophilane-type sesquiterpene (1) and twenty-five known compounds, i.e. eleven sesquiterpenes (2–12), one diterpene (13), one triterpene (14), one sterol (15), four flavonoids (16–19), one lignan (20), one cumarin (21), three phenylpropanoids (22–24), one benzene derivative (25), and one alkaloid (26). The structures of all isolated compounds were elucidated on the basis of extensive spectroscopic methods (HRESIMS, 1D and 2D NMR experiments), as well as by comparison with literature data. Among them, ten compounds (4–6, 8–9, 13, 16–17, 19, 26) were reported for the first time from the genus Ligularia. The chemotaxonomic significance of the isolated compounds is discussed.