Abstract In a search for structurally interesting substances from traditional Chinese medicines, eight compounds were isolated from an ethanolic extract of the stem bark of Daphne giraldii Nitsche. On the basis of one‐and two‐dimensional nuclear magnetic resonance and mass spectrometry data, and chemical methods, their structures were determined to be 2H‐1‐benzopyran‐2‐one‐8‐hydroxy‐7‐ O ‐β‐D‐glucopyranosyl‐5‐(2‐oxo‐2H‐1‐benzopyran‐7‐hydroxy‐8‐yloxy) (compound 1), 1‐pentanone, 1‐(4‐hydroxyphenyl)‐5‐phenyl (compound 2), octadecyl caffeate (compound 3), (+)syringaresinol‐4,4′‐diglycoside (compound 4), daphnetin‐8‐O‐β‐D‐glucopyranoside (compound 5), p‐hydroxybenzoic acid (compound 6), 7,7′‐dihydroxy‐[6, 8′‐bi‐2H‐benzopyran]‐2, 2′‐dione (compound 7), and daphnorin (compound 8), respectively. Of the compounds isolated, compounds 1 and 2, which we named daphnolin and daphnolon, respectively, were new, and the others were obtained from this plant for the first time. (Managing editor: Wei Wang)