Four new daphniphyllum alkaloids, namely daphnicalycines A–D (1–4), together with nineteen known related ones (5–7 and 11–26), were isolated from the stems and leaves of Daphniphyllum calycinum. Their structures including the absolute configurations were unambiguously elucidated by extensive spectroscopic analysis, X-ray diffraction analysis and comparison with the reported data. In particular, with the assistance of X-ray diffraction analysis, we were able not only, for the first time, to give full 1H and 13C NMR assignment of daphniteijsmanine (7) and to elucidate its absolute stereochemistry, but also lead to correct the structure of caldaphnidine E (9). The confusions reported for 1 and daphnimacropine (8) in the literature were also clarified. © 2020 Elsevier Ltd