This review gives an overview of the electrochemical investigations about the properties of various types of graphene composites in the ethanol oxidation. Various routes to provide appropriate graphene‐based materials required electrochemical techniques for investigation of different types of the materials as well as their performance and efficacy in ethanol oxidation are discussed in detail. Furthermore, it is demonstrated that the incorporation of suitable materials, e. g. noble metals (graphene‐supported binary and ternary metal nanoparticles), metal oxides, conductive polymer, etc, with graphene results in excellent electrocatalytic activity, superb durability and selectivity in ethanol oxidation. Immobilization of electrocatalytically active NPs on graphene supports using physical approaches is considered as an effective route to prepare direct ethanol fuel cell (DEFC) anode catalysts.