We present a general method for characterizing the intrinsic electrochemical properties of graphene sheets, such as the specific double-layer capacitance, in the absence of porosity-related artifacts and uncertainties. By assembling densely tiled monolayers of electrically insulating or conductive functionalized graphene sheets onto electrode substrates (gold and highly oriented pyrolytic graphite), we demonstrate our ability to isolate their intrinsic electrochemical response in terms of surface-specific double-layer capacitance and redox behavior. Using this system, the electrochemical properties of various types of graphene can be directly compared without the need to take into account changes in electrode morphology and electrolyte accessibility arising because of varying material properties.