An efficient method for pharmaceutically useful selenoflavones via a ruthenium-catalyzed selenylation reaction is demonstrated. The ruthenium-catalyzed selenylation was applied to synthesize diverse alkenyl selenides from simple unsaturated acids/amides and diaryl diselenides. A wide range of differently substituted diaryl diselenides can be applied in this protocol with a good functional group with excellent stereo- and regioselectivity.