Two novel alkaloids, paxdaphnidine A (1) with a unique pentacyclic skeleton and paxdaphnidine B (2) with an uncommon tetracyclic skeleton, were isolated from the stems and leaves of Daphniphyllum paxianum. Their structures were established by spectral methods, especially two-dimensional NMR techniques ((1)H-(1)H COSY, HSQC, HMBC, and NOESY).