The　influence　of　surface　modification　of　SiO2　carrier　by　grafting　method　and　its　effects　for　Rh　supporting　was　investigated　on　formaldehyde　hydroformylation　reaction.　The　relationship　between　the　structure　of　catalysts　and　their　performance　was　characterized　in　detail　by　X-ray　diffraction,　N2　adsorption–desorption,　temperature　programmed　reduction　with　H2,　X-ray　photoelectron　spectroscopy,　and　in　situ　infrared.　After　grafting　the　amino　organic　functional　group,　the　surface　circumstance　of　SiO2　was　altered,　and　moreover,　sites　available　for　metal　loading　was　enriched　on　the　carrier　that　distribute　a　high　dispersion　of　Rh　species　Under　the　same　Rh　loading,　the　Rh@N–SiO2　catalyst　exhibits　better　catalytic　activity　than　pristine　SiO2　supported　Rh　catalysts.　Spectroscopic　evidences　suggest　the　presence　of　an　electronic　perturbation　between　Rh　and　modified　SiO2　which　promotes　the　hydroformylation　of　formaldehyde　by　maintaining　Rh　at　proper　Rh0/(Rh3+　+　Rhδ+)　ratio.　Graphic　Abstract:　Diagram　of　the　effect　of　surface　modified　with　amino　group　on　metal　rhodium　loading.　[Figure　not　available:　see　fulltext.].　©　2021,　The　Author(s),　under　exclusive　licence　to　Springer　Science+Business　Media,　LLC,　part　of　Springer　Nature.