Four tropane alkaloids, including a new compound triuniamine A (3) a known compound 2,3-dihydrodarlingine (4) with previously unassigned relative configuration and two known compounds darlingine (1), 10-hydroxydarlingine (2) were obtained from the stems of the endemic Australian plant Triunia montana (Proteaceae). The structure and relative configuration of the stereogenic centers in triuniamine A was elucidated on the basis of 1D and 2D NMR spectroscopy and high-resolution mass spectrometry. The relative configuration of the four stereogenic centers in 2,3-dihydrodarlingine were established from ROESY correlations, and its absolute configuration assigned from comparison of its ECD spectrum with that of (+)-darlingine.