New cyclometalated ruthenium(II) complexes of the type [Ru(L)(CO)(EPh3)2] (L = di-anionic CNO- donor of 1-(biphenylazo)naphthol; E = P, As) have been synthesized by the reaction using [RuHCl(CO)(EPh3)3] (E = P, As) with 1-(biphenylazo)naphthol ligand (H2L). The 1-(biphenylazo)naphthol ligand and ruthenium complexes are characterized by analytical, spectral (FT–IR, UV–Vis, 1H NMR and 31P NMR) methods. The molecular structure of ruthenium complex 1 was further confirmed by single crystal X-ray diffraction method. The catalytic efficiency of ruthenium complex 1 was evaluated for the transfer hydrogenation of various ketones to alcohols with excellent conversion up to 99% in the presence of i-PrOH/KOH at 82 °C. © 2017 Elsevier B.V.