Here we report on a simple, catalyst-free route for obtaining highly versatile subsequent functionalization on Si nanowires and Si(111) substrates. The versatility of this approach allows subsequent functionalization not only for organic species but also for inorganic (nanomaterial) species. The method has the advantage of controlling, the density of reactive cross-linkers without affecting the stability of the Si samples and without having metallic (or catalyst) residues on the surface. This method also allows formation Of monolayers with a variety of termination groups and is expected to open up a. wide range of,opportunities for producing stable molecule based (opto)electronic and (bio)sensing devices Immobilization of inorganic nanomaterial on the Si, samples offers advanced opportunities in molecular switches, (bio)sensors, molecular Scale memory, and Si based nanoelectronic devices.