The new ligand 6,6′-dihydroxy-2,2′-bipyridyl (dhbp) was synthesized via its tautomer, and this provides an efficient route to novel metal complexes of dhbp. In ruthenium complexes of dhbp, these OH groups enhance water solubility and may play a role in aqueous transfer hydrogenation with formate/formic acid as the hydrogen source. A series of cationic catalysts, [(η6-arene)Ru(N,N)Cl]Cl (arene = cymene, C6Me6; N,N = bipyridyl with OH, OMe, or H at the 6- and 6′-positions), were synthesized, fully characterized, and tested for transfer hydrogenation activity in various polar protic media. In aqueous media (90/10 water/methanol), Ru complexes of dhbp outperform the other catalysts tested (all at 1 mol %), and high percentage conversion of aromatic ketones to the corresponding alcohols is observed in 6 h. The OH groups appear to be essential for use of water as a green solvent and can potentially allow for metal–ligand bifunctional catalysis.