The kinetics of oxidative addition (OA) of 4-chlorobenzotrifluoride to a well-defined Pd⁰-NHC complex, [Pd(IPr)(PhC≡CPh)], has been investigated using electrochemical techniques. The influence of the concentration of the substrate and added amounts of the weakly coordinating ligand on k_obs have been studied. The resulting OA product has been isolated and full characterized and is a dimeric species. Additionally, evidence supports a “cocktail-type” catalysis and the reductive elimination of the NHC ligand from the Pd center as a possible decomposition pathway. Finally, the influence of eight different NHC ligands on the oxidative addition has been evaluated.