Reduced graphene oxide/zinc oxide (rGO/ZnO) hybrid nanocomposites were prepared from synthesized GO and high energy ball milled (HEBM) ZnO for supercapacitor electrodes. Evolution of intrinsic point defects and defect-induced morphological, structural and size-dependent properties of rGO/ZnO hybrid nanocomposites were investigated using electron paramagnetic resonance (EPR) spectroscopy. CV, PEIS and GCPL techniques were employed to investigate the electrochemical behavior of the electrode materials and the effects of defects on the electrochemical performance of the electrodes by using the standard two-electrode cell in a 6 M KOH electrolyte. Analyses of the obtained CV and impedance profiles have shown the pseudocapacitive and EDLC-type contributions in the supercapacitors. Cycling stabilities were evaluated using galvanostatic charge-discharge curves at current densities between 0.10 and 2.40 A g-1. The capacitance retention of all electrodes was found to be 100% after 30 cycles at 0.30 A g-1. The electrochemical analyses revealed that the incorporation of ZnO that is rich in core defects improved the charge transfer performance and ion diffusion of the rGO electrode.