Silica　hollow　microspheres　with　moonscape-like　rough　surface　(RS)　and　macroporous　surface　(MS)　have　been　controllably　synthesized　by　a　water–oil–water　three-phase　emulsion　method,　which　are　used　as　supports　of　the　heterogeneous　catalysts　for　the　catalytic　hydrogenation　of　nitrile-butadiene　rubber　(NBR).　It　is　found　that　Pd　can　be　uniformly　dispersed　on　both　amino-functionalized　RS　and　MS　supports　and　both　the　catalysts　show　high　hydrogenation　activity　with　100%　selectivity　to　C=C　bonds.　However,　the　reusability　of　Pd/N-RS　is　much　better　than　that　of　Pd/N-MS,　maintaining　92%　of　activity　without　any　regeneration　treatment　after　five　times　of　recycling　experiment.　The　high　activity　retention　is　because　the　moonscape-like　surface　of　the　RS　support　is　favorable　for　the　contact　of　NBR　macromolecules　with　the　active　sites,　and　more　importantly,　the　NBR　macromolecules　do　not　need　to　diffuse　into　the　interior　of　the　catalyst,　leading　to　fast　desorption　of　the　hydrogenated　NBR　from　the　surface　of　catalyst　and　re-exposure　of　the　active　sites.　©　2020,　Springer　Science+Business　Media,　LLC,　part　of　Springer　Nature.