Ru^II-Complexes of chelating heteroditopic N-heterocyclic carbene ligands featuring imidazol-2-ylidene (ImNHC) and 1,2,3-triazol-5-ylidene (tzNHC) donors connected via a CH₂ spacer, 1a–c, were found to be very effective catalysts for the cross-coupling of secondary and primary alcohols with the elimination of H₂O. Diverse β-alkylated secondary alcohols were thus obtained by following this method in excellent yields of up to 95% by employing a very low catalyst (1a) loading of 0.01–0.001 mol% along with the inexpensive base KOH. Mechanistically, the present protocol follows the borrowing hydrogen strategy which was established by various control experiments including deuterium labelling experiments and importantly, ¹H NMR and ESI-MS analyses validated the participation of a Ru–H species in the catalytic cycle. Remarkably, the present system displayed the highest Ru-based TON of 396 000 for the β-benzylation of 1-phenylethanol with a catalyst loading of 1 ppm (0.0001 mol%). Additionally, diverse 2-alkylaminoquinoline derivatives were synthesized in a one-pot manner from 2-aminobenzyl alcohol, 2-arylacetonitrile, and various primary alcohols.