Ni-M (M = Y or La)-catalyzed hydrogenolysis of furfural (FFR) to produce 1,5-pentanediol (1,5-PeD) has been developed through the formation of tetrahydrofurfuryl alcohol (THFA) as an intermediate product. Ni(0)-Y2O3 or Ni(0)-La(OH)(3) composite catalysts executed cleavage of the C-O bond of THFA, giving 1,5-PeD with remarkably high selectivity. Consecutive reactions including hydrogenation of the C=O and C=C bonds and subsequent hydrogenolysis of the C-O bond were performed.