From the aerial part of Sambucus chinensis, a new megastigmane glucoside (1) was isolated, together with seven known compounds. The structure of compound 1 was elucidated by spectroscopic analysis together with the application of the modified Mosher’s method to be (3S,5R,6S,9R)-megastigman-5,6-epoxy-3,9-diol 9-O-β-D-glucopyranoside. The structure of a closely related compound, sammangaoside B, has been reinvestigated, and it was assigned as (3S, 5R, 6S, 9S)-megastigman-5,6-epoxy-3,9-diol 9-O-β-D-glucopyranoside. Therefore, compound 1 is a new compound from nature.