The spontaneous one-electron reduction of diazonium salts on hydride-terminated porous silicon (pSi) and flat silicon produces surface radicals that can be trapped chemically. These silicon radicals react with reagents such as alkyl/arylselenoethers, alkenes, alkynes, and alkylbromide groups to generate covalently bound functionalities in a manner analogous to the chemistry of molecular-based silicon radical species, prepared via different methods. When pSi is exposed to an acetonitrile solution of any of the three diazonium salts examined in this study, aryl groups from the diazonium precursor become covalently bound and significant oxidation is noted; if, however, a reactive trapping agent is added, such as an alkyl/arylselenoether or a carbon-carbon unsaturated bond, no aryl group attachment is observed and oxidation is circumvented due to the efficiency of the trapping chemistry. The reactions proceed rapidly, in less than 3 h to maximum coverage, at room temperature. The diazonium salt-initiated radical reaction with alpha,omega-alkenes and alkynes tolerates various functional groups including aryl, diene, diyne, carboxylic acid, and hydroxyl, reacting exclusively via the carbon-carbon unsaturated bond; alpha,omega-bromoalkenes are not, however, compatible with this chemistry. A silicon-based molecule, tris(trimethylsilyl) silane, in the presence of a diazonium salt initiator and a primary alkyne does not lead to the hydrosilylation product but to tris(trimethylsilyl) silylbromide and the hydrogenated arene, derived from the diazonium. The difference in reactivity between the molecule and the surface is due to the fact that the silicon surface is a source of electrons to reduce the diazonium salts to aryl radicals, whereas a heterolytic pathway is followed in the molecular silane case.