The first manganese complex bearing a chiral N-heterocyclic carbene (NHC) ligand was prepared and studied by spectroscopic methods and X-ray diffraction. While IR spectroscopy revealed the existence of two isomers in solution with distinct νCO band patterns, DFT calculations indicated that these isomers correspond to rotamers around the Mn−NHC bond and their different spectroscopic properties were rationalized by the occurrence of attractive π(C=C)⋅⋅⋅π*(C≡O) or σ(C−H)⋅⋅⋅π*(C≡O) intramolecular interligand interactions. The evaluation of this complex in catalytic hydrosilylation of acetophenone using Ph2SiH2 under UV irradiation led to the formation of the corresponding (R)-alcohol with low enantioselectivity.