The　heterogeneous　selective　hydrogenation　of　nitrile　butadiene　rubber　(NBR)　is　an　efficient　method　to　generate　high　value-added　hydrogenated　NBR.　Nevertheless,　the　inherent　large　molecular　size　and　high　spatial　hindrance　of　polymers　lead　to　poor　activity　and　metal　loss.　Herein,　we　report　a　simple　support　ammonia　pretreatment　strategy　for　the　synthesis　of　efficient　N-doped　Pd　catalyst　and　applied　for　the　NBR　hydrogenation.　The　results　reveal　that　N　doping　enhances　electron　transfer　from　the　support　to　Pd　more　effectively　than　oxygen-rich　vacancy　support,　thereby　substantially　enhancing　the　electron　cloud　density　and　stability　of　the　Pd　sites.　The　formation　of　more　electron-rich　Pd　sites　not　only　significantly　enhances　the　adsorption-activation　ability　of　C=C　and　H2,　but　also　lowers　the　apparent　activation　energy　of　the　reaction.　As　a　result,　the　Pd/N-TiO2-R　demonstrates　best　activity　with　a　hydrogenation　degree　(HD)　of　98　%　and　a　TOF　value　of　335　h−1,　significantly　higher　than　that　of　Pd/TiO2−R　(HD=83　%,　282　h−1)　and　Pd/TiO2　(HD=74　%,　204　h−1).　This　strategy　will　provide　new　inspiration　to　improve　the　activity　and　stability　of　Pd/TiO2　catalysts　for　the　hydrogenation　of　unsaturated　polymers.　©　2024　Wiley-VCH　GmbH.