Herein,　a　systematical　investigation　is　devoted　to　explore　nitrile　butadiene　rubber　(NBR)　hydrogenation　activity　and　selectivity　in　different　organic　solvents,　and　the　dependence　between　reactivity　and　solvent　is　revealed　with　the　assistance　of　the　density　functional　theory　(DFT).　The　results　show　that　the　electron-pair　donor　solvents　have　better　performance　in　NBR　hydrogenation　activity　than　the　weak　electron-pair　acceptor　solvents,　but　they　do　not　modify　the　selectivity　to　HNBR　that　always　keeps　up　to　100　%.　A　direct　correlation　between　reactivity　and　hydrogen　bond　acceptance　ability　(β)　is　discovered　in　both　solvent　families　and　the　higher　β,　the　better　hydrogenation　performance.　The　preferred　solvent　is　cyclohexanone　with　hydrogenation　degree　of　91.4　%　in　10　minutes　and　the　highest　conversion　of　94.2　%.　Our　contribution　is　to　provide　useful　information　about　solvent　and　solvent　effect　on　the　hydrogenation　of　NBR　and　gain　new　insight　into　NBR　hydrogenation　reaction　process.　©　2019　Wiley-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim