Commercial silybin (I) was oxidized to dehydrosilybin (II) employing iodine and KOAc in HOAc. Alkylation of (II) with geranyl bromide (III) in the presence of tetraethylammonium hydroxide provided a mixture of the desired 8-geranyl dehydrosilybin along with minor amounts of the 6-geranyl isomer (IV), which were separated by chromatography.