Calyciphylline G (1), a novel Daphniphyllum alkaloid with an unprecedented fused-hexacyclic skeleton containing a 5-azatricyclo[6.2.1.01,5]undecane ring, has been isolated from the stem of Daphniphyllum calycinum (Daphniphyllaceae), and the structure and relative stereochemistry were elucidated on the basis of spectroscopic data. © 2007 Elsevier Ltd. All rights reserved.