Two new Daphniphyllum alkaloids, 9,10-epoxycalycinine A (1) and homodaphniphyllate (2), together with eight known related alkaloids, were isolated from the stems and leaves of Daphniphyllum calycinum. The structures of the new compounds 1 and 2 were elucidated on the basis of in-depth spectroscopic-data analysis, by chemical derivatization, and by comparison of their spectroscopic data with those of known compounds.