<jats:title>Abstract</jats:title><jats:p>Two new daphniphyllum alkaloids named 2‐hydroxyyunnandaphnine D (<jats:bold>1</jats:bold>) and methyl 7‐hydroxyhomodaphniphyllate (<jats:bold>2</jats:bold>), together with eight known alkaloids, daphnioldhanin D, calyciphylline F, calyciphylline B, deoxycalyciphylline B, daphnicyclidin H, macropodumine C, 9,10‐epoxycalycine A, and yunnandaphnine A, were isolated from the stems and leaves of <jats:italic>Daphniphyllum calycinum.</jats:italic> Their structures and relative configurations were established on the basis of spectral evidence (including 2D‐NMR) and subsequently confirmed by a single‐crystal X‐ray crystallographic diffraction analysis.