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Exchange of one PCy₃ unit of the classical Grubbs catalyst 1 by N‐heterocyclic carbene (NHC) ligands leads to “second‐generation” metathesis catalysts of superior reactivity and increased stability. Several complexes of this type have been prepared and fully characterized, six of them by X‐ray crystallography. These include the unique chelate complexes 13 and 14 in which the NHC‐ and the Ru=CR entities are tethered to form a metallacycle. A particularly favorable design feature is that the reactivity of such catalysts can be easily adjusted by changing the electronic and steric properties of the NHC ligands. The catalytic activity also strongly depends on the solvent used; NMR investigations provide a tentative explanation of this effect. Applications of the “second‐generation” catalysts to ring closing alkene metathesis and intramolecular enyne cycloisomerization reactions provide insights into their catalytic …