Graphene and graphene nanoplatelets can be functionalised via a gas-phase thermochemical method; the approach is versatile, readily scalable, and avoids the introduction of additional defects by exploiting existing sites. Direct TEM imaging confirmed covalent modification of single layer graphene, without damaging the connectivity of the lattice, as supported by Raman spectrometry and AFM nano-indentation measurements of mechanical stiffness. The grafting methodology can also be applied to commercially-available bulk graphene nanoplatelets, as illustrated by the preparation of anionic, cationic, and non-ionic derivatives. Successful bulk functionalisation is evidenced by TGA, Raman, and XPS, as well as in dramatic changes in aqueous dispersability. Thermochemical functionalisation thus provides a facile approach to modify both graphene monolayers, and a wide range of graphene-related nanocarbons, using variants of simple CVD equipment.