Formation of metal nanoparticles on silicon substrate by thin gold film irradiation with accelerated atomic and molecular ions is shown. Structures obtained were etched by metal-assisted catalytic chemical technique to get porous silicon structure. Size of gold nanoparticles and the structure of porous siliconstrongly depend on kind of incident species and ion dose. A local increase in the energy release density at the target surface that takes place during molecular ion bombardment significantly reduce the doses required for the formation of predetermined film morphology and the distribution of nanoparticles on the surface, while at the same time molecules exhibit lower radiation effect on the substrate. Luminescent properties of porous silicon do not depend on the kind of ion used, and can be tuned by composition of an etching solution