α-MnO2 has been made using a solid state synthesis and the specific surface area then modified through milling. The formation of α-MnO2 (specific surface area 96m2 g−1) has been studied by SEM and powder XRD prior to milling. Electrode films (cast using MnO2, graphite and PVDF) have been investigated using N2 sorption at 77K and show a more complex relationship than their parent oxides. Specific capacitances of 235Fg−1 were observed in cyclic voltammetry studies in (NH4)2SO4 (aq.) electrolyte. Good cyclability was observed in hybrid C/MnO2 cells investigated through both galvanostatic and electrochemical impedance techniques. The specific capacitances of the cells were found to correlate with S BET of the electrode films and not that of the parent MnO2 powders.