It has been established that a newly developed cyclopentadienyl rhodium(III) CpARhIII complex, bearing an acidic secondary amide moiety on the Cp ring, is able to catalyze the ortho‐bromination of O‐phenyl carbamates with N‐bromosuccinimide (NBS) at room temperature. The presence of the acidic secondary amide moiety on the CpA ligand accelerates the bromination by the hydrogen bond between the acidic NH group of the CpA ligand and the carbonyl group of NBS. Makes it faster! It has been established that a newly developed cyclopentadienyl rhodium(III) CpARhIII complex, bearing an acidic secondary amide moiety on the Cp ring, is able to catalyze the ortho‐bromination of O‐phenyl carbamates with NBS at room temperature. The hydrogen bond between the acidic NH group of the CpA ligand and the carbonyl group of NBS accelerates the bromination.