Orophea hexandra Blume (Annonaceae) from Gunung Gede, Bogor, West Java, was studied. Previously, only one publication existed on the genus Orophea, and no work had been reported on O. hexandra. A methanolic extract from its leaves (364 g dry weight) was prepared, subjected to alkaloid extraction, and examined by gas chromatography-mass spectrometry (GC-MS). Three alkaloids—asimilobine, N-methyllaurotetanine, and reticuline—were identified by comparison with authentic material (mass spectrum and retention index). Four further alkaloids—isoboldine, N-nornuciferine, pronuciferine, and N-methylcrotonosine—were tentatively identified by comparison of their mass spectra with literature data. The alkaloids of O. hexandra, mostly of the isoquinoline type, correspond to those isolated from other members of the Annonaceae, having chemotaxonomic significance.