A non-destructive and versatile chemical reduction method was used to dissolve and subsequently brominate few-layer graphene sheets (FLGs); the direct covalent attachment of bromine to the graphene framework was demonstrated by X-ray photoelectron spectroscopy (XPS). The brominated few-layer graphenes (FLG-Br) provide a convenient, stable, liquid-phase precursor, suitable for the synthesis of a variety of directly functionalised graphenes. As an example, the FLG-Br species was used to initiate atom transfer radical polymerisation (ATRP), to obtain poly(methyl methacrylate) (PMMA)-grafted graphene (FLG-PMMA), which was six times more dispersible in acetone than controls. In addition, the FLG-Br is active for nucleophilic substitution reactions, as illustrated by the preparation of methoxypolyethylene glycol (mPEG)- and OH-substituted derivatives. The products were characterised by thermogravimetric analysis coupled with mass spectrometry (TGA-MS), XPS and Raman spectroscopy. Grafting ratios (GR) for these polymer-grafted materials varied between 6 and 25%; even at these GRs, all graphene derivatives showed increased solubility in organic solvents.