This chapter provides an overview of current research on electrochemical supercapacitor materials fabricated by the layer-by-layer assembly technique. Emphasis has been given towards the basic principle of supercapacitors and various electrode materials suitable for high-performance supercapacitor applications. The chapter is a detailed discourse regarding the layer-by-layer fabrication technique with their performance and stability. Electrode materials such as metal oxides/hydroxides and conducting polymers exhibit pseudocapacitive behavior whereas carbon-based materials show electrical double layer capacitance. Electrode materials such as, graphene, graphene oxide, carbon nanotubes, polyaniline, and carbon nanofibers, provide high surface area for the layer-by-layer deposition of metal oxides, metal hydroxides, conducting polymers that aid the effective ion diffusion and which in turn enhances the specific capacitance with excellent cyclic stability.