The trideuteriomethylation of BH vertices in CB11H12− and its derivatives with CD3OTf (OTf=triflate, trifluoromethanesulfonate) yields a mixture of BCD3 and BCHD2 substitution products, thus demonstrating the intermediacy of a species with a long enough lifetime for hydrogen scrambling between the boron vertex and the methyl substituent. No such scrambling is observed if CD3OTf is used to methylate toluene. According to density functional theory calculations, the intermediate in BH vertex methylation is a three-center bonded σ adduct of a methyl cation to the BH bond and the proton scrambling occurs via a transition structure containing a distorted square-pyramidal methane attached axially to a “naked” boron vertex. The subsequent proton or deuteron loss is presently not understood in detail. A general comparison of electrophilic substitution on closo-boranes and arenes is provided and similarities as well as differences are discussed. A recalculation of the optimized geometry of the CB11Me12. radical produced a second Jahn–Teller distorted minimum and resulted in a somewhat improved agreement between calculated and measured proton hyperfine coupling constants.