A phytochemical investigation of Blighia unijugata led to the isolation of eleven hederagenin glycosides. Among these compounds, six are previously undescribed, two are described in their native forms for the first time and three are known whereas firstly isolated from Blighia unijugata. The structure of the undescribed compounds was elucidated on the basis of 2D NMR and mass spectrometry analyses as 3-O-β-D-xylopyranosyl-(1 → 3)-α-L-arabinopyranosyl-(1 → 4)-β-D-glucopyranosyl-(1 → 3)-α-L-rhamnopyranosyl-(1 → 2)-α-L-arabinopyranosylhederagenin, 3-O-β-D-xylopyranosyl-(1 → 3)-α-L-arabinopyranosyl-(1 → 4)-3-O-acetyl-β-D-glucopyranosyl-(1 → 3)-α-L-rhamnopyranosyl-(1 → 2)-α-L-arabinopyranosylhederagenin, 3-O-β-D-glucopyranosyl-(1 → 3)-α-L-arabinopyranosyl-(1 → 4)-β-D-glucopyranosyl-(1 → 3)-α-L-rhamnopyranosyl-(1 → 2)-α-L-arabinopyranosylhederagenin, 3-O-β-D-xylopyranosyl-(1 → 3)-β-D-xylopyranosyl-(1 → 4)-β-D-glucopyranosyl-(1 → 3)-α-L-rhamnopyranosyl-(1 → 2)-α-L-arabinopyranosylhederagenin, 3-O-β-D-xylopyranosyl-(1 → 3)-β-D-xylopyranosyl-(1 → 4)-3-O-acetyl-β-D-glucopyranosyl-(1 → 3)-α-L-rhamnopyranosyl-(1 → 2)-α-L-arabinopyranosylhederagenin, 3-O-α-L-arabinopyranosyl-(1 → 4)-β-D-glucopyranosyl-(1 → 3)-α-L-rhamnopyranosyl-(1 → 2)-α-L-arabinopyranosylhederagenin 28-O-β-D-glucopyranosyl-(1 → 6)-β-D-glucopyranosyl ester, 3-O-α-L-arabinopyranosyl-(1 → 4)-β-D-glucopyranosyl-(1 → 3)-α-L-rhamnopyranosyl-(1 → 2)-α-L-arabinopyranosylhederagenin 28-O-β-D-glucopyranosyl ester and 3-O-β-D-xylopyranosyl-(1 → 4)-β-D-glucopyranosyl-(1 → 3)-α-L-rhamnopyranosyl-(1 → 2)-α-L-arabinopyranosylhederagenin 28-O-β-D-glucopyranosyl ester. These results revealed the existence of several conserved structural features that could be used as chemotaxonomic markers for the Blighia genus such as the glycosidic sequence 3-O-α-L-arabinopyranosyl-(1 → 4)-β-D-glucopyranosyl-(1 → 3)-α-L-rhamnopyranosyl-(1 → 2)-α-L-arabinopyranosyl, the occurrence of 3-O-acetylated β-D-glucopyranosyl units and the systematic presence of hederagenin as aglycone.