An electrochemical method is reported for the production of graphene oxide (GO) and graphene nanosheets using the following steps: electrochemical intercalation of cetyltrimethylammonium bromide (CTAB) into graphite followed by the electrochemical exfoliation of a CTAB-intercalated graphite electrode. These electrochemical processes yield a stable colloidal GO/CTAB suspension. Then, exfoliated GO was used as a precursor at cathodic potentials (completely reduced potential: −1.5 V) by cyclic voltammetry or cronoamperometry. The colloidal GO/CTAB suspension and electrochemically reduced graphene oxide (RGO) nanosheets have been carefully characterized by spectroscopic and electrochemical techniques in comparison to the stable colloidal graphene/sodium dodecyl sulfate suspension. Particularly, FTIR spectra indicate that a variety of the oxygen-containing functional groups have been produced from the graphite plane by electrochemical oxidation. UV-vis spectra of GO/CTAB suspensions show that a large amount of GO is obtained after successive electrochemical intercalation and exfoliation processes. Finally, the straightforward synthesis of RGO/CTAB composites provide a low-cost and high performance for oxygen reduction reaction (ORR), which is also a promising strategy for the synthesis of various GO/cationic surfactants composites.