The electrochemical behavior of colloidal solutions of graphene oxide (GO) is described here in detail. The GO reduction is shown to exhibit near-reversible electron transfer on Pt electrodes, based on E1/2 and ΔEp values. The observed peak current is found to depend linearly on the concentration of the GO and the square root of the scan rate, suggesting that the response is diffusion-limited. The difference between the experimental and diffusion-only limited theoretical current values suggests that migration may be hindering mass transport to the electrode surface. Varying the type and concentration of the supporting electrolyte showed that mass transport is weakly influenced by the presence of negative charges on the graphene particles. The effect of pH on GO was also investigated, and it was found that the reduction peak heights were directly related to proton concentration in acidic solutions. On the basis of the results presented here, we propose that the observed response of GO on Pt electrodes is a result of the reduction of protons from the colloidal double layer. This difference is observed only because the Pt electrode surface can efficiently catalyze proton reduction.