Cyclopentanone　(CPO)　is　a　high-value　platform　chemical　widely　used　in　fuel,　fragrances,　and　polymers,　yet　its　sustainable　production　from　biomass　remains　challenging.　This　work　addresses　this　gap　by　developing　efficient　Ni/TiO2　catalysts　through　crystal　phase　engineering　of　TiO2　supports　(anatase,　rutile,　mixed-phase　P25)　for　aqueous-phase　hydrogenative　ring-rearrangement　of　furfural　(FAL)　to　CPO.　Crucially,　the　TiO2　phase　dictates　the　Ni-O-Ti　interface　structure,　governing　nickel　speciation　and　reactivity.　Ni　supported　on　mixed-phase　P25　achieves　exceptional　performance　under　industrially　relevant　conditions:　91.1%　FAL　conversion,　89.3%　CPO　selectivity,　and　specific　rate　of　71.6　h(-1),　surpassing　catalysts　on　pure　anatase　(9.1%　conversion)　or　rutile　(55.8%　conversion).　Physical　mixture　experiments　confirm　this　superiority　stems　from　the　intrinsic　interface　of　P25,　not　component　blending.　Characterization　reveals　that　P25　stabilizes　a　multifunctional　surface　ensemble:　metallic　Ni-0　(18.0%　by　XPS)　enables　hydrogenation,　while　cationic　Ni2+　facilitates　acid-catalyzed　dehydration　and　ring　rearrangement.　Simultaneously,　sufficient　metal-support　interaction　permits　in　situ　regeneration　of　active　sites.　The　optimized　1Ni/P25　demonstrates　robust　stability　over　five　cycles　with　retained　selectivity　(＞90%),　showcasing　practical　durability.　This　study　provides　a　scalable　design　strategy-support　crystal　phase　tuning-to　engineer　cost-effective,　multifunctional　catalysts　for　industrial　biomass　upgrading,　advancing　green　manufacturing　of　cyclic　ketones　without　precious　metals.