A facile pathway to [RuCl₂(η⁶-benzocrownether)]₂ complexes is described and crystal structures of the complexes [RuCl₂(η⁶-benzo-15-crown-5)]₂ and [RuCl₂(η⁶-dibenzo-18-crown-6)]₂ are reported. The complexes were derivatised with (1S,2R)-2-amino-1,2-diphenylethanol and evaluated in the enantioselective transfer-hydrogenation of acetophenone. The effect of complexation of different alkaline metals (Na, K, Cs) within the crown on the selectivity and reaction rate was studied. Interaction of a sulfonated phosphine ligand with the crown was probed by NOESY-NNIR and utilisation of the crownether to serve as an anchor for catalyst immobilisation was investigated.