The design and fabrication of chiral nanostructures is a promising approach to realize enantiomeric recognition and separation. In our work, gold nanorod@chiral mesoporous silica core–shell nanoparticles (GNR@CMS NPs) have been successfully synthesized. This novel material exhibits strong and tunable circular dichroism signals in the visible and near-infrared regions due to the optical coupling between the CMS shells and the GNR cores. When chiral cysteine molecules are loaded in the porous shells, the corresponding surface enhanced Raman scattering spectroscopy demonstrates a distinct chiral recognition effect, which can be used to semiquantitatively measure the composition of chiral enantiomers. A detailed sensing mechanism has been disclosed by density functional theory calculations.