Here we explore the exceptional structural characteristics of a set of graphene-related materials prepared by a wet chemical approach. We present a comprehensive study of the effects of morphology, sonication, temperature, probe species, and stacking behaviour on the measurement of graphene surface area. Nitrogen gas was used in the solid state gas adsorption measurements and methylene blue dye for adsorption measurements on aqueous dispersions of graphene. The surface area values obtained are among the highest reported for synthetic graphenes: 1700 m2 g- 1 in aqueous dispersions and 612 m2 g- 1 in the solid state. Microscopy revealed the graphene used in the study was present in large part as free sheets and electron diffraction confirmed the successful synthesis of high quality graphene with a regular C-C bond length of 1.41 ± 0.02 Å.