<jats:title>Abstract</jats:title><jats:p>The new pyrrolizidine alkaloid glycoside <jats:bold>1</jats:bold>, and the three new highly oxygenated bisabolane sesquiterpenes <jats:bold>4</jats:bold>–<jats:bold>6</jats:bold>, together with the two known pyrrolizidine alkaloids <jats:bold>2</jats:bold> and <jats:bold>3</jats:bold>, were isolated from the roots of <jats:italic>Ligularia cymbulifera</jats:italic> (W. W. <jats:sc>Smith</jats:sc>) <jats:sc>Hand</jats:sc>.‐<jats:sc>Mazz</jats:sc>. Their structures were established on the basis of spectroscopic analysis, especially 1D‐ and 2D‐NMR data. The cytotoxic activities of compounds <jats:bold>1, 2</jats:bold>, and <jats:bold>4</jats:bold>–<jats:bold>6</jats:bold> were evaluated against hepatoma (BEL‐7402), human leukemia (HL‐60), human ovarian carcinoma (HO‐8910), and nasopharyngeal carcinoma (KB) cell lines (<jats:italic>Tables 1–3</jats:italic>). Compound <jats:bold>6 s</jats:bold>howed weak cell‐growth inhibition of BEL‐7402 cell.