Five new polycyclic Daphniphyllum alkaloids, macropodumines F (1) and G (2), 17-oxoyuzurimine (3), and macropodumines H (4) and I (5), were isolated from the leaves of D. macropodum MIQ., collected in Sichuan Province, China. The structures and relative configurations of the new compounds as well as of four known, related alkaloids - were elucidated on the basis of in-depth spectroscopic and mass-spectrometric analyses, by chemical derivatization, and by comparison of spectroscopic data with those of known compounds.