Naphthyl-derived orthometalated RuII-NHC complexes have been developed for catalytic applications considering the stereoelectronic profiles of the NHC ligands, which can be modified easily via alteration of the NHC donors (ImNHC/1,2,4tzNHC) as well as their substitution pattern at the naphthyl ring. The azolium salts [(2a−c)-H]Br, precursors for the NHC ligands, react with [Ru(p-cymene)Cl2]2 in the presence of a base to deliver the ortho-metalated RuII-NHC complexes 3a−c with the general formula [(NHC)Ru(p-cymene)Br]. Orthometalation in these complexes can be exploited for further functionalization of the NHC ligands. This is depicted by the generation of the diphenylethylene-inserted isolable intermediate complex 4, from the reaction of 3a with diphenylacetylene in a 1:1 ratio, which eventually provides an annulated salt 5a-Br via reductive elimination. Gratifyingly, this process can also be made catalytic, which directly provides several mono-/bis-annulated cationic N-heterocyclic compounds starting from the imidazolium salts [(2a,b)-H]Br using [Ru(p-cymene)Cl2]2 as a precatalyst. Furthermore, subtle variations in the electronic profiles of the complexes 3a−c in combination with steric alterations are observed to influence their activity in the transfer hydrogenation of acetophenone, a model for the hydride transfer process. Among all the complexes studied here, complex 3b with an ImNHC donor at the second position of the naphthyl ring was identified as a superior catalyst in comparison to 3a,c featuring either a different NHC donor or substitution pattern with a low loading of 0.1 mol%. © 2020 American Chemical Society