A novel Daphniphyllum alkaloid, oldhamiphylline A (1), together with five known alkaloids, deoxycalyciphylline B, deoxyisocalyciphylline B, calyciphylline, secodaphniphylline, and calycicine A, was isolated from the leaves of Daphniphyllum oldhami. The structure of 1 was established by spectroscopic methods, especially 2D NMR techniques (1H,1H-COSY, HMQC, HMBC, and NOESY).