An in situ electrochemical electron paramagnetic resonance (EPR) spectroscopic study of N-doped reduced graphene oxide (N-rGO) is reported with the aim of understanding the properties of this material when employed as an electrical double-layer capacitor. N-rGO shows a capacitance of 100 F g−1 in 6 M KOH, which is twice that found for reduced graphene oxide (rGO). The temperature dependence of the rGO EPR signal revealed two different components: a narrow component, following the Curie law, was related to defects; and a broad curve with a stronger Pauli law component was attributed to the spin interaction between mobile electrons and localised π electrons trapped at a more extended aromatic structure. The N-rGO sample presented broader EPR signals, indicative of additional contributions to the resonance width. In situ EPR electrochemical spectroscopy was applied to both samples to relate changes in unpaired electron density to the enhanced capacitance. The narrow and broad components increased and diminished reversibly with potential. The potential-dependent narrow feature was related to the generated radical species from corresponding functional groups: e.g. O- and N-centred radicals. Improved capacitive formation by the N-modified basal graphene planes can be accordingly suggested to underlie the enhanced capacitance of N-rGO in basic electrolytes.