Superelectrophilic silylium/arenium ions are shown to be highly effective H/D exchange promoters for the exhaustive deuteration of electron-deficient aryl halides. Several of the resulting perdeuterated aryl halides have been previously inaccessible with existing deuterium-labeling procedures. Using inexpensive C6D6 as the deuterium source, excellent degrees of deuterium incorporation were achieved under ambient reaction conditions. Importantly, the perdeuteration remains unaffected on multigram scale, even at a reduced catalyst loading of 0.1 mol %. By this method, otherwise expensive or noncommercially available NMR solvents such as 1,2-dichloro- and 1,2-difluorobenzene can be prepared.