| Summary: | ‘Globemaster’ is an ornamental hybrid cultivar whose parent plants are <i>Allium cristophii</i> and <i>A. macleanii</i>. The chemical constituents of ‘Globemaster’ bulbs have not yet been examined; thus, a systematic phytochemical investigation was undertaken herein. A series of chromatographic separations of the MeOH extract of ‘Globemaster’ bulbs afforded 27 steroidal glycosides (<b>1</b>–<b>27</b>), which are classified into 23 spirostanol glycosides (<b>1</b>–<b>8</b> and <b>11</b>–<b>25</b>), two furostanol glycosides (<b>9</b> and <b>26</b>), a pregnane glycoside (<b>10</b>), and a cholestane glycoside (<b>27</b>). The structures of the hitherto undescribed compounds (<b>1</b>–<b>10</b>) were determined from the two-dimensional NMR spectroscopic data and hydrolysis. The cytotoxicity of the isolated compounds (<b>1</b>–<b>27</b>) toward HL-60 human promyelocytic leukemia cells, A549 human adenocarcinoma lung cancer cells, and SBC-3 human small-cell lung cancer cells was evaluated. Compounds <b>8</b>, <b>22</b>, <b>23</b>, <b>24</b>, and <b>26</b> exhibited cytotoxicity toward all cell lines in a dose-dependent manner, with IC<sub>50</sub> values in the 1.3–49 µM range.
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