Phytochemical investigation on the aerial parts of Trachelospermum dunnii led to the isolation and identification of 16 compounds, including nine dibenzylbutyrolactone lignans (1–9), two furanoid lignans (10–11), one dihydrobenzofuran lignan (12), one aryltetralin lignan (13), two flavonoids (14–15), and one phenolic compound (16). The structure of compound 1 was elucidated by means of spectroscopic analyses, including HRESIMS, and 1D and 2D NMR experiments. Compounds 1–16 are reported from title plant for the first time, while compounds 1–2, 10–12, and 14–16 have not been recorded previously in genus Trachelospermum. The dibenzylbutyrolactone lignans may serve as chemotaxonomic markers of T. dunnii. •Sixteen metabolites are isolated from Trachelospermum dunnii (H.Lév.) H. Lév.•Compounds 1–16 are first time isolated from the species Trachelospermum dunnii.•Compounds 1–2 and 9–16 are the first report from the genus Trachelospermum.•Dibenzylbutyrolactone lignans could be considered as chemotaxonomic markers for genus Trachelospermum.