Extensive phytochemical investigation on the whole herbs of Delphinium anthriscifolium var. majus led to the identification of fourteen diterpenoid alkaloids, including three new C20–diterpenoid alkaloids (anthriscifolsines A–C, 1–3), six new C19–diterpenoid alkaloids (anthriscifolrines A–F, 4–9), and five know compounds (10–14). Among them, anthriscifolsine A represents a novel C20–diterpenoid alkaloid characterized by a seco C–ring. The structures of the isolated compounds were elucidated by extensive spectroscopic methods, including HR-ESI–MS, X–ray, and 1D and 2D NMR experiments. Bioactivity of compounds 3–6 was evaluated for their cytotoxicity against the MCF–7, HepG2 and H460 cancer cell lines.