We have described a regiodivergent methodology for the selective deuteration of indoles. Directing-group-free palladium-catalysis in the presence of deuterated acetic acid allows for hydrogen isotope exchange at the C2 and C3 position with high levels of deuterium incorporation. Reaction of these compounds with K2CO3 and a protic solvent selectively yields C2-deuterated products. Metal-free, acid-mediated deuteration instead affords selective isotope incorporation at C3 only. The methodology not only allows for selective, regiodivergent latestage deuteration of drug targets (as demonstrated on pindolol/ Visken). On a more fundamental level, the selectivity observed in the palladium-catalyzed transformations may guide the development of more complex C-H activation methodology on indoles and other nitrogen heterocycles.