<jats:title>Abstract</jats:title><jats:p>One new alkaloid, named caldaphnidine H (<jats:bold>1</jats:bold>), together with eight known ones, daphnioldhanin G (<jats:bold>2a</jats:bold>), methyl homosecodaphniphyllate (<jats:bold>3</jats:bold>), daphnezomine M (<jats:bold>4</jats:bold>), daphniyunine A (<jats:bold>5</jats:bold>), calyciphylline A (<jats:bold>6</jats:bold>), deoxycalyciphylline B (<jats:bold>7</jats:bold>), deoxyisocalyciphylline B (<jats:bold>8</jats:bold>), and calyciphylline B (<jats:bold>9</jats:bold>) was isolated from the leaves and stems of <jats:italic>Daphniphyllum calycinum.</jats:italic> The structure of <jats:bold>1</jats:bold> was established by spectral methods, especially 2D‐NMR techniques. The structure of daphnioldhanin G (<jats:bold>2b</jats:bold>) reported previously was revised to <jats:bold>2a</jats:bold> mainly by single‐crystal X‐ray diffraction and spectral analysis.