In term of new carbon-based material, graphene quantum dots(GQDs) are a boundless promising electrode material for energy storage devices due to their excellent properties of large specific surface area, high conductivity, excellent transparency and unique fluorescence characteristics. GQDs form composites with metal compounds or carbon material to construct three-dimensional spatial structures, which is conductive to electron diffusion and ion transport, greatly improving the practical application performance of GQDs as electrode materials. Furthermore, heteroatoms-doped GQDs can provide more active sites and enhance the utilization of active substance. Herein, The synthesis strategies of GQDs, which are mainly classified into top-down and bottom-up methods,are briefly introduced. The effects of various preparation methods on the particle size, surface defect sites and fluorescence characteristics of GQDs are also distinct. The applications of GQDs, doped GQDs and their composites in energy storage devices such as supercapacitors, lithium ion batteries, solar cells and fuel cells in recent years, it is obvious that GQDs-based electrode materials with quantum confinement effect and boundary effect have great potential for new energy storage devices. The influence of distinctive space structure on electrochemical properties are analyzed. In addition, it is pointed out that the future development of GQDs is to find a rapid, green and environmentally-friendly method for mass synthesis of GQDs, uniform and effective doping or compounding and constructing a unique spatial structure of electrode materials, which can further improve the electrochemical performance in the applications of energy storage devices.