A new alkaloid, daphnilongeridine (1), together with six known alkaloids, daphmacropodine (2), daphmacrine (3), codaphniphylline (4), daphniyunnine A (5), daphniyunnine C (6), and daphniyunnine E (7), were isolated from the leaves and stems of Daphniphyllum longeracemosam. The so far elusive configuration at C(25) of daphmacropodine (2) was assigned on the basis of ROESY correlations.