We use ab initio density functional calculations to study the chemical functionalization of single-wall carbon nanotubes and graphene monolayers by silyl (SiH(3)) radicals and hydrogen. We find that silyl radicals form strong covalent bonds with graphene and nanotube walls, causing local structural relaxations that enhance the s p(3) character of these graphitic nanostructures. Silylation transforms all carbon nanotubes into semiconductors, independent of their chirality. Calculated vibrational spectra suggest that specific frequency shifts can be used as a signature of successful silylation.