We report the synthesis of ruthenium metathesis catalysts containing unsymmetrical N-trifluoromethyl NHC ligands. These complexes have been fully characterized, and a Ru–F interaction has been identified in the solid state by X-ray crystallographic analysis for three catalysts with Ru–F distances between 2.629(2) and 2.652(2) Å. The influence of the N-trifluoromethyl NHC ligands on the initiation rates and activation parameters was studied. The activity of these catalysts was evaluated in benchmark olefin metathesis reactions and compared to the standard second-generation Grubbs catalyst. Remarkably, N-trifluoromethyl catalysts display an unusually high selectivity for the formation of terminal olefins (up to 90%) in the ethenolysis of ethyl oleate. Much improved selectivity is demonstrated for alternating copolymerization of cyclooctene and norbornene as well. These results underline the importance of electronic effects exerted by the NHC ligand.