[structure: see text] Two new complex polycyclic alkaloids, macropodumines D (1) and E (2), both possessing unprecedented skeletons, along with four known related alkaloids, were isolated from the leaves and barks of Daphniphyllum macropodum Miq. The structures including the relative stereochemistry of new compounds 1 and 2 were elucidated on the basis of detailed spectroscopic data analysis.