Electrochemical reduction of CO2 to CO is an interesting topic. In this work, we prepared metal-free electrodes by depositing graphene oxide (GO), multi-walled carbon nanotube (MWCNT), and GO/MWCNT composites on carbon paper (CP) using electrophoretic deposition (EPD) method. The electrodes were characterized by different methods, such as X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The electrochemical reduction of CO2 to CO was conducted on the electrodes in 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF4)/acetonitrile (MeCN) electrolyte, and the composition of the electrolyte influenced the reaction significantly. It was demonstrated that GO/MWCNT-CP electrode was very effective for the reaction in IL (90 wt%)/MeCN binary mixture, the Faradaic efficiency of CO and current density were even higher than those on Au and Ag electrodes in the same electrolyte.