The invention discloses preparation of a silane coupling agent-modified SiO2 loaded rhodium catalyst and a selective hydrogenation application of the catalyst to butadiene-acrylonitrile rubber. The method comprises the following steps: (1) carrier modification, namely, modifying SiO2 by utilizing a silane coupling agent with an amino group in an organic solution or water so as to obtain modified SiO2; and (2) loading catalyst preparation, namely, adding the modified SiO2 into a rhodium solution, standing, washing and drying so as to obtain the loaded catalyst APTS (aminopropyltriethoxysilane)-SiO2-Rh. The prepared catalyst is used for nitrile butadiene rubber (NBR) hydrogenation research, and the hydrogenated butadiene-acrylonitrile rubber with the hydrogenation strength being more than 98% can be obtained. The preparation process is simple, and the adopted reaction raw materials are wide in source scope and small in toxicity and are economic and practicable. The NBR hydrogenation research shows that the hydrogenation efficiency is greatly improved, the hydrogenation strength is improved to above 98% from the original 52% under the same condition, and moreover, the recycling performance of the catalyst is also greatly improved after the reaction is ended. The APTS-SiO2-Rh is a high activity recycled NBR hydrogenation heterogeneous catalyst and is beneficial to HNBR (hydrogenated butadiene-acrylonitrile rubber) large-scale production.