In this paper, an electrochemical approach was described for preparing graphene with different microstructures, starting from aqueous solutions of graphene oxide (GO), processed under direct voltage. The process relied on the electrochemical reduction of GO sheets deposited on the surface of Cu electrode. The same electrode is first used as the anode for the electrophoretic deposition of GO film, and then as the cathode, allowing for the effective reduction of GO. Paper-like graphene was observed on the electrode after the reduction, while crumpled graphene existed in the solution, which could be further transformed to graphene scroll by sonication. The samples were characterized by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The results showed that the oxygen functional groups are significantly removed after the reduction. The mechanism for this method was also proposed in this paper. Moreover, a scale-up device was designed to make this method more applicable for commercialization. This method has the potential for large-scale production of graphene.