Chromatographic fractionation of bark extracts from Simira glaziovii (Rubiaceae) afforded the steroids β-sitostenone, stigmastenone, β-sitosterol and stigmasterol, methyl trans-4-hidroxy-3-methoxycinamate (1), the alkaloids harmane (2) and the new stereoisomer of ophiorine B (3). The structures were established by 1H and 13C NMR, including 2D techniques and mass spectral analysis, of the natural products and pentaacetyllyalosidic acid (4a) and β-carboline monoterpene tetraacetylglucoside (5, 1,22-lactamlyaloside) derivatives obtained by chemical transformations.