To achieve high selectivity in directed C–H activation, an NHC ligand was introduced to a palladium catalyst. A range of Pd‐PEPPSI complexes were applied in the direct acetoxylation of 2‐phenylpyridine. The best catalyst was found to be the one based on a diisopropylphenyl‐substituted NHC ligand, and this was successfully used for the functionalization of sp2 as well as more challenging sp3 bonds for a broad variety of substrates. The explored method showed a highly improved selectivity compared to previously reported results with up to 96 % yield for the monoacetoxylated product. Kinetic studies show that sterics of the catalyst is less important in dictating conversion and selectivity; despite an induction period, it was shown that the catalyst is molecular in nature.