The　C2-O　cleavage　of　furanic　ring　is　the　crucial　step　in　selective　hydrogenation　of　furfuryl　alcohol　(FOL)　to　1,5pentanediol　(1,5-PDO).　In　this　study,　reduced　mixed　Ni-Co-Al　metal　oxide　catalysts　with　rich　oxygen　vacancy　(Ov)　and　different　Co/Ni　molar　ratios　were　prepared　through　intercalation　modification　of　Co-based　hydrotalcite　by　ammonium　citrate　(CA),　followed　by　calcination　and　reduction.　The　catalytic　performance　exhibited　that　a　quantitative　conversion　of　FOL　with　44.4　%　yield　and　8.2　mmol1,5-PDO　&　sdot;gcat　-1　&　sdot;h-　1　productivity　of　1,5-PDO　were　achieved　by　using　Co2Ni1Al1Ox-CA(0.1)　(molar　ratio　of　Co:Ni　=　2:1;　molar　concentration　ratio　of　CA:Na2CO3　=　0.1)　under　optimal　conditions.　The　stability　test　showed　that　Co2Ni1Al1Ox-CA(0.1)　consistently　rendered　above　40　%　yield　of　1,5-PDO　in　seven　consecutive　cycles.　Catalyst　characterizations　were　carried　out　using　a　series　of　techniques　including　XPS,　EPR,　O2-TPD,　etc.　The　results　demonstrate　that　the　addition　of　CA　effectively　altered　the　surface　molar　ratios　of　Co2+/(Co2++Co3+),　thereby　regulating　the　Ov　content　of　the　obtained　catalysts.　The　CoO-Ov　sites　in　the　catalyst　might　enhance　the　adsorption　of　FOL　by　eta　1-(O)-alcoholic　model,　which　weakened　C2O　bond　on　the　furanic　ring　of　FOL.　Besides,　the　H2-TPD　anslysis　confirmed　that　the　enhanced　spillover　of　hydrogen　from　Ni0　onto　CoO-Ov　site,　thereby　promoting　the　cleavage　of　the　C2-O　bond　in　FOL　and　subsequent　hydrogenation　of　enol　intermediates.　In　addition,　the　DFT　calculations　imply　that　FOL　adsorption　on　CoO-Ov　site　by　eta　1-(O)-alcoholic　model　was　significantly　favorable　than　that　on　pristine　CoO　sites　(-1.68　eV　versus　-1.55　eV).　Consequently,　this　study　has　substantiated　the　crucial　role　played　by　CoO-Ov　in　the　reaction　pathway　leading　to　1,5-PDO　formation　via　FOL,　proposing　a　viable　scheme　for　designing　catalysts　based　on　transition　metals　and　elucidating　their　underlying　reaction　mechanism.