Electrochemical energy-storage devices such as batteries and supercapacitors are important components in emerging portable electronic device, electric vehicle, and clean energy storage and supply technologies. This review describes recent progress in the development of nanostructured electrodes, the main component of the electrochemical energy-storage device, prepared by layer-by-layer (LbL) electrostatic assembly. Major advantages associated with, and challenges to, the fabrication of LbL electrodes, as well as the future outlook for expanding the application of LbL techniques, are discussed.