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.