In　order　to　improve　enzyme　immobilization　performance　of　SiO2　carrier　materials,　homemade　hierarchical　mesoporous　SiO2　hollow　microspheres　were　modified　with　amino　groups　by　grafting　and　in-situ　methods,　respectively.　Their　application　in　papain　immobilization　was　investigated.　Compared　with　unmodified　samples,　primary　most　probable　pores　(8.68-8.70　nm)　of　the　grafting　modified　microspheres　decrease　and　secondary　most　probable　pores　(29.30-29.89　nm)　do　not　change　significantly,　which　indicates　that　the　amino　groups　are　mainly　grafted　in　primary　pores.　Both　primary　(4.47-7.34　nm)　and　secondary　most　probable　pores　(14.49-19.78　nm)　decrease　significantly　after　modification　via　the　in-situ　method,　which　indicates　that　amino　groups　are　modified　in　both　areas.　The　maximum　papain　immobilization　amount　and　its　corresponding　relative　enzyme　activity　of　the　in-situ　modified　samples　were　750　mg·g-1　and　121.0%,　respectively,　which　were　higher　than　those　modified　by　grafting　and　unmodified　samples.　In-situ　amino　modification　has　advantages　in　improving　enzyme　immobilization　performance　of　SiO2　carriers.　©　2022　Zhejiang　University.　All　rights　reserved.