This paper presents the first report of the successful ball-milling exfoliation of graphitic filaments (GANF^® carbon nanofibres) into single layer graphene. The addition of small amounts of solvent during the milling process makes it possible to enhance the intercalation of the exfoliating agent (melamine) between the graphene layers, thus promoting exceptional exfoliation. Advantage has also been taken of the fact that the Hansen solubility parameters of graphene are different from those of carbon fibres, which allows single and few-layer graphene to be suspended in a particular solvent, thus discriminating them from poorly exfoliated carbon nanofibres.