Silica nanotubes can serve as high aspect ratio templates for the deposition of inorganic nanoparticles to form novel hybrids. However, the nature of the interfacial binding is still an unresolved challenge when considered at the atomic level. In this work, novel nanocomposites have been successfully fabricated by the controlled nucleation and assembly of Sb2S3 nanoparticles on the surface of mercaptopropyl-functionalized silica/polymer hybrid nanotubes (HNTs). The Sb2S3 nanoparticles were strongly attached to the HNTs surface by interactions between the pendent thiol groups and inorganic sulfur atoms. Detailed analysis of the geometric and electronic structure using first–principle density functional theory demonstrates charge transfer from the nanoparticles to the underlying HNTs at the Sb2S3/HNTs interfaces. Formation of a packed array of Sb2S3 nanoparticles on the HNTs results in mixing of the electronic states of the components, and is mediated by the mercaptopropyl bridges between Sb2S3 and the outer layer of the HNTs.