[structure: see text] The first diamino Daphniphyllum alkaloid, daphnipaxinin (1), with an unprecedented hexacyclic fused skeleton, along with a known alkaloid, daphnicyclidin A (2), was isolated from the stem of Daphniphyllum paxianum Rosenth. The structure and absolute stereochemistry of 1 were established by spectral methods, especially two-dimensional NMR techniques and CD analysis.