Four new Daphniphyllum alkaloids, daphnilongeranins A-D (1-4), along with four known ones, daphniphylline, longistylumphylline A, deoxyisocalyciphylline B, and daphnicyclidin D, were isolated from the leaves and stems of Daphniphyllum longeracemosum. Daphnilongeranin A (1) is the first seco-10,17-longistylumphylline A type Daphniphyllum alkaloid, and daphnilongeranin B (2) is a new C-22 nor-Daphniphyllum alkaloid based on a new C21 skeleton. Their structures and stereochemistry were determined using spectroscopic data and chemical methods.