<jats:title>Abstract</jats:title><jats:p>In this study, four types of compounds including coumarins, chromones, furoylmethyl amino acid derivative and benzofuran glycoside were isolated from the roots of <jats:italic>Saposhnikovia divaricata</jats:italic>. The electrospray ionization (ESI) mass spectral fragmentation pathways of these compounds were proposed. In particular, the ESI‐MS<jats:sup>n</jats:sup> fragmentation behavior of linear dihydrofurocoumarins, dihydrofuro‐ and dihydropyranochromones were deduced in detail. For the linear dihydrofurocoumarins, the fragmentation was triggered by the initial loss of the C‐4′ substituting group. Then, the characteristic ions were observed followed by the losses of 15, 18, 28 and 46 Da. It is noteworthy that the elimination of H<jats:sub>2</jats:sub>O (18 Da) from the cleavage of the dihydrofuran ring is reported for the first time. For the linear dihydrofurochromones, characteristic eliminations of 18, 48 and 72 Da were observed. The loss of 18 Da could arise from two different fragmentation pathways, and the observed ion was composed of a mixture of two different structural ions. For the linear dihydropyranochromones, it was found that the dihydropyran ring was converted into the pyran ring by the elimination of the C‐3′ substituting group. This fragmentation was followed by the diagnostic losses of 18, 28, 42 and 54 Da in tandem mass spectrometry. The above fragmentation rules were successfully applied for the analysis of the chemical constituents of the roots of <jats:italic>Saposhnikovia divaricata</jats:italic>. A total of 32 compounds were identified or tentatively characterized by HPLC/DAD/ESI‐MS<jats:sup>n</jats:sup>. Among them, eight compounds were new and seven compounds were reported from that genus for the first time. Copyright © 2008 John Wiley & Sons, Ltd.