A novel white light-promoted reaction using photoluminescent nanocrystalline silicon enables the hydrosilylation of alkenes and alkynes, providing stabilization of the porous silicon without significant loss of the photoemissive qualities of the material. Photopatterning and lithographic fabrication of isolated porous silicon structures are made possible. Experiments and observations are presented which indicate that the light promoted hydrosilylation reaction is unique to photoluminescent silicon, and does not function on nonemissive material. Hydrosilylation using a reactive center generated from a surface-localized exciton is proposed based upon experimental evidence, explaining the photoluminescence requirement. Indirect excitons formed by light absorption mediate the formation of localized electrophilic surface states which are attacked by incoming alkene or alkyne nucleophiles. Supra-band gap charge carriers have sufficient energy to react with nucleophilic alkenes and alkynes, thereupon causing Si-C bond formation, an irreversible event. The light-promoted hydrosilylation reaction is quenched by reagents that quench the light emission from porous silicon, via both charge transfer and energy transfer pathways.