A Ni-Y2O3 catalyst containing ruthenium (Ru/Ni-Y2O3) was synthesized and applied to the hydrogenolysis of tetrahydrofurfuryl alcohol (THFA) to produce 1,5-pentanediol (1,5-PeD), which showed superior catalytic performance over that of the Ni-Y2O3 catalyst itself. The optimized ruthenium-containing catalyst, which was prepared by impregnation of 1.0 wt% ruthenium in Ni-Y2O3, showed high catalytic activity for producing 1,5-PeD, giving an 86.5% yield at 93.4% conversion of THFA under 2.0 MPa of H-2 at 423 K after 40 h. The formation of Ru-Ni-0-Y2O3 boundaries was proposed to accelerate the C-O bond scission of the tetrahydrofuran ring to give 1,5-PeD.