<jats:title>Abstract</jats:title><jats:p>A novel <jats:italic>Daphniphyllum</jats:italic> alkaloid, oldhamiphylline A (<jats:bold>1</jats:bold>), together with five known alkaloids, deoxycalyciphylline B, deoxyisocalyciphylline B, calyciphylline, secodaphniphylline, and calycicine A, was isolated from the leaves of <jats:italic>Daphniphyllum oldhami.</jats:italic> The structure of <jats:bold>1</jats:bold> was established by spectroscopic methods, especially 2D NMR techniques (<jats:sup>1</jats:sup>H,<jats:sup>1</jats:sup>H‐COSY, HMQC, HMBC, and NOESY).