Heterogeneous　hydrogenation　of　nitrile　butadiene　rubber　(NBR)　is　a　pivotal　technology　for　producing　high-value-added　hydrogenated　NBR,　yet　the　complex　macromolecular　configuration　poses　critical　challenges　to　catalyst　activity　and　stability.　Herein,　metal-doped　M-TiO2　(M　=　Mo,　V,　Mn　species)　nanosheet　supports　featuring　aerobic-stable　oxygen　vacancies　(Vo)　and　Ti3+　sites　were　engineered,　and　loaded　with　Pd　for　NBR　hydrogenation.　Among　the　dopants,　Mn　species　exhibits　optimal　charge　compensation　effect,　achieving　the　lowest　Vo　formation　energy　(1.73　eV)　and　highest　Vo-Ti3+　density　(25.8%　Vo,　27.1%　Ti3+),　outperforming　V　(3.38　eV;　18.1%　Vo,　17.2%　Ti3+)　and　Mo　(4.03　eV;　15.5%　Vo,　12.7%　Ti3+).　These　Vo-Ti3+　sites　enhance　the　dispersion　and　stability　of　Pd,　endowing　Pd　with　electron-rich　characteristics　which　synergistically　strengthen　C[dbnd]C　and　H2　adsorption-activation　process　while　reducing　the　activation　energy　barrier.　As　a　result,　Pd/Mn-TiO2　exhibits　excellent　catalytic　activity　(97%)　and　TOF　value　(306　h−1)　for　NBR　hydrogenation,　surpassing　Pd/V-TiO2　(94%,　268　h−1),　Pd/Mo-TiO2　(86%,　245　h−1),　and　Pd/TiO2　(75%,　204　h−1).　This　work　elucidates　the　role　of　high-valence　metal　doping　on　TiO2　defect　engineering,　establishing　a　universal　design　principle　for　durable　macromolecular　hydrogenation　catalysts.　©　2025　Elsevier　B.V.