Carbon-based materials have attracted a great deal of attention in recent years for electrochemical CO2 reduction reaction (CO2RR). This contribution gives an overview of recent experimental and theoretical efforts in designing carbon-based materials for CO2RR and provides hints for further tuning the electronic structure of carbon-based materials for highly efficient CO2RR catalysis. Using combined density functional theory (DFT) calculations and experimental evidence, we show that graphene-based materials without embedded metal atoms exclusively reduce CO2 to CO. We also show that in order to see any post CO reduced products, the presence of metal atoms is essential. By examining a variety of metal-doped at single vacancy of graphene, we demonstrate facile reduction of CO to methane.