Material with a core-shell structure based on a porous silica core and Ag nanoparticles (AgNPs) as shell (SiO@Ag) was prepared with the seed growth method. Cellulose derivatives as chiral selectors were coated on the surfaces of SiO@Ag particles by means of coating and intermolecular polycondensation as chiral stationary phases (CSPs), respectively. Fifteen racemates were used to evaluate their chiral recognition ability by high-performance liquid chromatography (HPLC). The results implied that the CSPs based on SiO@Ag particles obtained stronger interaction with the analytes leading to better enantioseparation due to the existence of AgNPs on the surfaces of silica gel, compared with a cellulose derivative-modified silica column. In addition, the new CSPs showed special selectivity for ketone enantiomers, and AgNPs played a synergistic effect with cellulose derivatives on enantioseparation. Graphical abstract Schematic of SiO@Ag stationary phase.