Nanostructured materials provide new and exciting approaches to the development of supercapacitor electrodes for high-performance electrochemical energy storage applications. One of the biggest challenges in materials science and engineering, however, is to prepare the nanomaterials with desirable characteristics and to engineer the structures in proper ways. This dissertation presents the successful preparation and application of very promising materials in the area of supercapacitor energy storage, including manganese dioxide and its composites, polyaniline and activated carbons. Attention has been paid to understanding their growth process and performance in supercapacitor devices. The morphological and electrochemical cycling effects, which contribute to the understanding of the energy storage mechanism of MnO2 based supercapacitors is thoroughly investigated. In addition, MnO2 based binary (MnO2-carbon nanocoils, MnO2-graphene) and ternary (MnO2-carbon nanotube-graphene) nanocomposites, as well as two novel electrodes (MnO2-carbon nanotube-textile and MnO2-carbon nanotube-sponge) have been studied as supercapacitor electrode materials, showing much improved electrochemical storage performance with good energy and power densities. Furthermore, a general chemical route was introduced to synthesize different conducting polymers and activated carbons by taking the MnO2 nanostructures as reactive templates. The electrochemical behaviors of the polyaniline and activated nanocarbon supercapacitors demonstrate the morphology-dependent enhancement of capacitance. Excellent energy and power densities were obtained from the template-derived polyaniline and activated carbon based supercapacitors, indicating the success of our proposed chemical route toward the preparation of high performance supercapacitor materials. The work discussed in this dissertation conclusively showed the significance of the preparation of desirable nanomaterials and the design of effective nanostructured electrodes for supercapacitor energy storage applications.