The new chiral diphosphine ligand [(5, 6),(5′, 6′)-bis (1, 2-ethylenedioxy) biphenyl-2, 2′- diyl] bis (diphenylphosphine)(BisbenzodioxanPhos) has been successfully prepared and used in ruthenium-catalyzed asymmetric hydrogenation of 2-(6′-methoxy-2′-naphthyl) propenoic acid and β-keto esters with high enantioselectivity (92.2% and up to 99.5% ee, respectively).