Unprecedentedly high-density (up to 79 wt%) immobilization of monodispersed gold nanoparticles (AuNPs) within mesoporous silica SBA-15 is achieved by variation of their pore size and pore-pore connectivity to enable a full access of AuNPs to the large and high-affinity internal surface of mesoporous silica (MPS) SBA-15. In addition, according to the adsorption kinetics, dipole-induced dipole interaction is suggested to be the primary driving force for adsorption of AuNPs on silica. Interestingly, the high internal surface of MPS shows much higher affinity to AuNPs than the external surface. The optical properties of these densely immobilized AuNPs are also investigated, demonstrating that a plasma coupling exists between closely spaced AuNPs.