Deuterium labeled compounds find widespread application in life science. Herein, the deuteration of electron-rich (hetero)aromatic compounds employing B(C6F5)3 as the catalyst and D2O as the deuterium source is reported. This protocol is highly efficient, simply manipulated, and successfully applied in the deuteration of 23 substrates including natural neurotransmitter-like melatonin. It is assumed that the weakening of the O-D bond ultimately results in the formation of electrophilic D+.