In the recent years, a rapid increase in the global energy consumption persuades scientists to develop new eco-friendly energy storage devices. Within the context of energy storage, electrode design plays a significant role by providing high surface area, fast electron mobility, high electrical conductivity and good chemical stability to attain high electrochemical performance. Graphene with its outstanding properties like high electrical conductivity and large surface area, became an extremely versatile carbon material for high performance energy storage devices. However, one of the important issues is to prevent the agglomeration of graphene sheets in the structure since the aggregation of graphene sheets and their crumbling lead to a significant decrease in electrical conductivity and surface area, and this affects negatively the utilization of graphene in energy applications. To overcome this problem, twodimensional (2D) graphene sheets are converted into various macroscopic graphene structures through different techniques such as CVD and self-assembly method. However, it is not easy to control the size, shape and hollowness of the obtained structures and these techniques are not cost-effective. At this point, co-axial electrospinning process has received great attention due to its ability to produce core-shell structures with controlled dimensionality. In this study, graphene based polymeric composites with different morphologies of sphere, foam, and fibers were fabricated through one-step core-shell electrospraying/electrospinning technique. The effect of different metal/metal oxides on the electrochemical performance of the fabricated composite electrodes has been investigated in details. To fully understand the effect of graphene on the structure and electrochemical activity of electrodes, two different types of graphene including thermally exfoliated graphene oxide and graphene nanoplatelets were added to the fibers based on the number of graphene layers and surface oxygen functional groups. The highest specific capacitance of 454 F/g was observed in case of polyaniline coated manganese oxide/graphene platelets embedded fibers at a scan rate of 1 mV/s. Consequently, by combining the advantages of graphene-based structures such as porous and interconnected network, high electrical conductivity, with the high electrochemical activities of transition metal oxides and conductive polymers, graphene-based hybrid composites became an ideal candidate as high-performance electrode materials to be utilized in various energy devices.