AbstractA series of neutral and cationic RhIII‐hydride and RhIII‐ethyl complexes bearing a NHC ligand has been synthesized and evaluated as catalyst precursors for H/D exchange of styrene using CD3OD as a deuterium source. Various ligands have been examined in order to understand how the stereoelectronic properties can modulate the catalytic activity. Most of these complexes proved to be very active and selective in the vinylic H/D exchange, without deuteration at the aromatic positions, displaying very high selectivity toward the β‐positions. In particular, the cationic complex [RhClH(CH3CN)3(IPr)]CF3SO3 showed excellent catalytic activity, reaching the maximum attainable degree of β‐vinylic deuteration in only 20 min. By modulation of the catalyst structure, we obtained improved α/β selectivity. Thus, the catalyst [RhClH(κ2‐O,N‐C9H6NO)(SIPr)], bearing an 8‐quinolinolate ligand and a bulky and strongly electron‐donating SIPr as the NHC, showed total selectivity for the β‐vinylic positions. This systematic study has shown that increased electron density and steric demand at the metal center can improve both the catalytic activity and selectivity. Complexes bearing ligands with very high steric hindrance, however, proved to be inactive.