Two new daphniphyllum alkaloids named 2-hydroxyyunnandaphnine D (1) and methyl 7-hydroxyhomodaphniphyllate (2), 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 Daphniphyllum calycinum. 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.